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FRANKLIN INSTITUTE LIBRARY 


PHILADELPHIA 


Class.G.6./..2 Book LTE Accession.../.G..2.L Aa 


Given by... lg.1. A222. boBlildhA22 72 


DIGEST OF PATENTS 


Relating to 


COAL-TAR DYES AND 
ALLIED COMPOUNDS 


United States patents issued 
prior to January 1, 1924 


, Prepared DY, 
’ s oo 2", go 2° 


an - - 5 > ” ) s © 


fee. “AIDA: ME GONLE 2 3 2 4c) 2. 


Special Agent, Bureau of the Census 


DEPARTMENT OF COMMERCE, 
BUREAU OF THE CENSUS, 
Washington, March 25, 1924. 


I hereby certify that, the following report is a true and complete transcript of the data gathered 
and compiled for use in “Digest of Patents Relating to Coal-Tar Dyes and Allied Compounds,”’ the 
original of which is in the files of the Bureau of the Census, U.S. Department of Commerce. 


W. M. STEUART, Director. 


Publication of the above-named report by The Chemical Publishing Company is hereby authorized. 
HERBERT HOOVER, Secretary of Commerce. 


EASTON, PENNSYLVANIA, U. S. A. 
THE CHEMICAL PUBLISHING COMPANY 
1926 


PREFACE 


DIGEST OF PATENTS RELATING TO COAL-TAR DYES 
AND ALLIED COMPOUNDS. 


This digest contains abstracts of patents issued prior to 
January I, 1924, arranged by chemical groups. The abstracts 
are thoroughly indexed according to name of patentee, name 
of assignee, color produced on fiber, and by intermediates em- 
ployed in the process of manufacture. A cross reference index 
giving corresponding numbers and names in the German work 
by Schulz (“Farbstofftabellen,” 1914) is included. 

The digest was begun in December, 1917, in the Color 
Laboratory of the Bureau of Chemistry, U. S. Department of 
Agriculture, at the suggestion of one of the leading coal-tar 
dye manufacturers, work being continued at intervals for a 
little over a year until abstracts to date were finished. Later 
the work was resumed and the digest completed in the Bureau 
of the Census, Department of Commerce, the author being em- 
ployed by that Bureau in connection with the census of manu- 
factures as an expert on the subject of chemicals and allied 
industries. 


FE Eg Ace 


CONTENTS 


Page 
INTRODUCTION 
Outline of work). co 6 oe oa nade ole sw ee oa wan tise a IV 
Abbreviations 35.0006. 4605 <4}. 0 ou dale a yeecn a ee play ho ee V 
Chemical nomenclature . .. 4.5.4 005 neta pli ole okies oe V 
PATENT ABSTRACTS 
Coal-tar dyes: 
Group T—Acridin . 2.0.29. 00004002 0 I 
Group II.~Anilin. black 0... 00. dese sa sas 6 5 
Group TT.—Anthraquinone- ... 025. 26. 92) ie. 8 
Group 1V:—Auramin= «0.45% ss sine aes Sak pe ST ott 61 
Group V.—Azin, including indulin ...... ..7 .a.aes ee 61 
Group VI—AZ0 oi ed a ee alk aie ld. Hee oe 67 
Group. VIlL—Indigo and indigoid ..:......... 32 eee 190 
Group  VIII.—Indophenol...3)%.5094.......445. eee 226 
Group TX.~-Nitro oi. bee iei ee cue os cere «chee aay 
Group Se NIEFOSO uly ates oe eet PR ee 230 
Group KU ——OXAZIN. oi css ce ele os 0's wre ip ae ane 231 
Group: > All Pyrazolone {9.2 an oe so 6 Si dee etki alguna aa 240 
Group XII]—Quinolin ~.... 0 202... e ess 243 
Group’ XIV.—Stilbeme oc... 0c 56 yous bss ss ue 245 
Group SV. piltur Soeur: Re Ae 247 
Group . XVI—Thiazin 22. 6... 5 ose cs. oe ce ee 281 
Group ‘XVIT.—Thiobenzenyl. 6. 0) a. ss oe os i 284 
Group X VIII.—Triphenylmethane, etc. ..........2.. 0) =e ee 285 
Group “XIX.—Xanthone (02.05 5.00.0. /s,0% 40 = bee 304 
Allied Compounds: 
Group. XX.—Mineral dyes .........) i. 1. 3, 25 eee Pre or 311 
Group XX1—Vegetable and petroleum dyes |... 2... 6se ee 314 
Group XXIJII.—General processes and intermediates ................. 317 
Group XXIII.—Applications, by dye groups and in general ........... 392 
Group XXIV.—Finished products other than dyes ...........5....... 443 
Explosives (€) 00. $0.2 sa0 2) 443 
Flavors and perfumes (f) ¢.). .¢.00) eae 445 
Medicinals (m) ..2..3....2: 545 5 ope 448 
Photo chemicals (p) ... 2.24.40 ee  heetOr 
Plastics (pl) 2... seed. A 470 
Tannins (t) 0 o.....< cesses 2 oe see 476 
INDEXES 
Assignee index 2.0... oeedee ea ceca es cee any tines 5 oa Hine ce se ene 478 
Color index’. 6.6 o sc ee ba eee ene dee oo a W sin ok oy 6 ont Seele glrr 483 
Intermediate andes’ <5 Guy ao eg eee oe ee MO Oy 496 
Patéentee Index vidas ca dee ee bet ce meen 3 aie aes eo as One nee nn 532 


Schulz index! (1914) 2.6 ac cbc cece ode wd ovine pitt o 8a en 577 


DIGEST OF PATENTS RELATING TO COAL-TAR 
DYES AND ALLIED COMPOUNDS-’* 


INTRODUCTION 


Outline of work.—The patents covered by this digest* have been gathered from 
all available sources, including classes and subclasses of the United States Patent 
Office bearing upon chemicals and allied products; Schulz’ Survey of the Coal-Tar 
Dyes, (1914); Winther’s “Patente der organischen Chemie;” Dr. Seaman’s list of 
coal-tar colors and lists furnished by dye manufacturing companies, as well as 
patent citations gathered from other sources. Classifications of abstracts follow 
commonly accepted chemical groups. No divisions of the main dye groups have 
been made, since multiplicity of subdivisions increases the difficulty in locating 
patents, and raises questions as to accuracy of classification in a subject of ex- 
treme flexibility. 

When a patent claims the application of a dye to fiber, as a mordant or de- 
veloped dye, or as a lake or printing compound, and there is no patent for the 
dye as such, the abstract is included with the dye series. If, however, the dye 
is the subject of a patent, and there is also a patent for an application process or 
compound of the dye, the second abstract is placed with applications Group XXIII. 
Where products are known, but their dyeing properties have not been previously 
ascertained, the patent necessarily takes the form of application to the fiber, but 
is herein grouped with the dyes. When a patent claims only an intermediate, and 
indirectly the derived dye, either in the title or the text of the patent, the abstract 
is grouped with dyes. 

A large number of patents claim both process and product, while some cover 
one or the other or both, in separate patents. In the abstracts, each patent is con- 
sidered as process-product, whether both are claimed or not, and therefore two 
separate patents for process and for product are practically duplications. Foot- 
notes accompanying abstracts explain conditions. 

The general form of presentation of the information in the abstracts is fairly 
obvious, but certain features may need explanation. Differences between claims 
and title are shown in parentheses on line. with the title. Following this the 
chemical constitution of the product except in Groups VI and XV is expressed 
as clearly as possible without employing graphic formulas. Then follows an out- 
line of the process and the properties of the product, as given in the patent. The 
number and name of the dye as it occurs in Schulz’ Survey of the Organic Color- 
ing Matters, (1914 edition) is placed at the bottom of the abstract together with 
cross references to other patents, notes, and remarks. 

In outlining the process of manufacture, intermediates appear with chief 
function in bold-faced type as an aid in referring to them in the Intermediate In- 
dex. When several processes and intermediates are mentioned in the patent, not 
more than two or three are cited, either in abstract or index. Brief reference is 


1 All patents, under the present law, expire 17 years from the date of original issue. 

2See Vol. X, Twelfth Census of the United States,—Manufactures, Part IV, for Digest of 
Patents relating to Chemical Industries issued prior to Jan. 1, 1902—particularly Group XI, 
Dyestuffs and Extracts, artificial, organic, pp. 879-909, and Carbon Compounds, subgroup Nitro- 
gen compounds, pp. 962-966. ‘ 


Vi INTRODUCTION 


made to additional materials, to variations in process conditions, and to one or 
more intermediates, with a general class reference, such as “ANILIN, and other 
aryl amins” or “1-Chlor ANTHRAQUINONE-2-aldehyde, or deriv.,” or “2-Amino- 


3-methyl-ANTHRAQUINONE, isomer or homolog,” or in some cases simply “or 
other,” to indicate that other similar compounds are enumerated in the patent. In 


the Intermediate Index, these will appear under the specific intermediate and under 
the class designation. 

Abbreviations. Much has been omitted concerning processes of a self-evident 
character. The main steps in the synthesis are noted, but filtration, precipitation, 
purification, drying, cooling, diluting, salting out, the kind of acid or alkali and the 
oxidizing or reducing agents used, frequently are not specified. Such phrases as 
“the separated product” or “the dried and purified material” imply that the suc- 
ceeding operation requires the product to be isolated at this point. This may 
mean one or a series of operations. 

In general, abbreviations of common words are used as in Chemical Abstracts, 
Journal of the American Chemical Society. Standardized phrases are used, in 
abbreviated form, especially with respect to properties of dyes. Superlative terms 
for fastness or other properties are ignored. The fibers, wool, silk, or cotton, are 
not mentioned in connection with dyeing properties, as the method of application 
indicates the kind of fiber. General reference to acids, alkalies, or caustic implies 
diluted solutions unless strength is specified. Parts means parts by weight; 
strengths of solutions are expressed in per cent or degrees Baumé; specific gravity 
is shown by figures in parentheses; temperatures are reported in degrees centigrade. 

In giving the properties of dyes, letters in parentheses following names of re- 
agents show the color of the solution or precipitate. The customary method of 
employing the initial letter or abbreviation of a color has been followed—violet 
(V), blue (B), green (G), yellow (Y), orange (O), red (R), brown (Br), black 
(Bk), and gray (Gy), with combinations for modifiers, such as green-gray (GGy), 
violet-red (VR), etc. 

Modifiers of color shade take the nearest secondary or primary color, for 
example, violet-blue, not reddish blue; orange-yellow, not reddish yellow; orange- 
red, not yellow red; violet-red, not bluish red. Violet is used in all cases for 
purple, orange-red for scarlet or scarlet red, and violet-red for magenta red. The 
termination “ish” for modifiers has been omitted—blue-green, not bluish green; 
green-yellow, not greenish yellow; etc. 

Dyes have been classified in relation to their application to the fiber into acid, 
acid mordant, basic, basic mordant, direct, developed, and reducing and sulfide vat. 
In addition there are lake making and oil soluble dyes. To some extent the classes 
overlap. Acid mordanting methods include the usual addition of dyes to previously 
mordanted fiber, the after treatment of dyed fiber with a mordant (after chroming, 
coppering, etc.,) and the one bath or metachrome process. Developed dyes include 
those capable of coupling with diazo compounds on the fiber or of diazotation on 
the fiber and developing with a coupling agent (ice colors, ingrain colors, etc.) ; 
those developed by oxygen of the air (Anilin Black) or oxidized by chemical salts 
such as chromates or copper compounds and by after treatment with formaldehyde. 
Vat dyes are roughly separated into reducing or hydrosulfite vat, and sulfur or 
sulfide vat, but sulfur dyes though frequently precipitated from NazS solvent and 
applied as reducing vat colors, are included among sulfide vat dyes. 

Chemical nomenclature.—In the use of chemical terms the rules adopted by 
the American Chemical Society in chemical abstracts have been followed, modified 
somewhat in accordance with common usage and for brevity, in order to make the 
digest as concise as possible without sacrificing clearness. 


INTRODUCTION vii 


99 «66 9» 66 ” 
’ 


Names of compounds ending in “ane,” “ene,” “ole,” when the vowel has the 
long sound, retain the final “e.” So also with the ending “ine” when pronounced as 
in “line;’ but with amin, anilin, toluidin, benzidin, etc., the final “e” has been 
omitted. “Oxy” is used for “hydroxy;” “o” has not been employed to separate 
syllables except as usage has sanctioned it; “sulfo” and “carbo” are used for sul- 
fonic and carboxylic acids; salts and esters are given as the free acid or base. 

The Intermediate index is a subject index with chief functions or index com- 
pounds arranged alphabetically. This chief function is shown in the index and 
the patent abstracts by bold-faced letters. 

Choice of chief function and order of precedence of substituents follow com- 
mon usage, index compounds being made as comprehensive as practicable. Sub- 
stituents that precede the index compound in the abstract follow the index com- 
pound in the index. For example—“4’/-Oxy phenyl 1-NAPHTHYLAMIN sulfo,” 
appears in the index as “I-NAPHTHYLAMIN, 4’-Oxy phenyl, sulfo.” 


A certain amount of standardization of nomenclature and of numbering was 
necessary, and all compounds were made to conform to such chosen standards. 
This necessitated some very careful work, the importance of which can readily 
be recognized. When the order of substituents or their positions was not clear, 
or was lacking in the patent, information in regard thereto was entered unaltered 
in the abstract and in the index. Numerals to designate positions of substituents 
with periods and hyphens to separate them have been employed, and Greek letters 
avoided as far as possible. 


The work has been brought down to January 1, 1924. 


PATENT ABSTRACTS. 


Dyes are classed in accordance with their final character. Anthraquinone derivs. 
fused in Na,S, etc., to convert into reducing vat colors are placed with suLFuR dyes. 
Pyrazolone derivs. used in usual way as coupling agents are to be found among 
Azo colors. 


COAL-TAR DYES. 
Group I.—ACRIDIN, 


382,832—May 15, 1888. Christian Rupo.pH, Germany. (Oehler.) 
Production of yellow coloring-matter. (Product also claimed.) Diamino ditolyl acridin. 

Hydro diamino ditolyl AcrIDIN is oxidized by air or preferably by slowly acting agents such 
as FeCl, in dil. HCl soln., containing ZnCl, to ppt. metal salt. YELLow direct and basic mordant 
dye. . 
S. 605.—“Benzoflavin.”” Note 395,080. 


395,080—Dec. 25, 1888. Christian RupoLtpH, Germany. (Ocehler.) 
Coloring-matter. 4-Amino benzoflavin. 

Hydro acripin base is dissolved in dil. HCI containing ZnCl, to which twenty per cent soln. 
of FeCl, is slowly added. Green YELLOW basic mordant dye. 

Near S. 605.—‘‘Benzoflavin.”’ Addition to 382,832. 


503,305—Aug. 15, 1893. Fritz BEnpER, Germany. (Leonhardt.) 
Orange dye. Tetra methyl diamino acridin or homologs. 

3-Amino dimethyl ANn1ILIN, or other substituted meta diamin, or dimethyl anilin, etc., is con- 
densed in alc. HCl with ForMALDEHYDE, benzaldehyde or formic acid (oxalic acid and glycerin) 
separated product further condensed by heating at 150° in autoclave with aq., leuco dye oxidized 
in HCl soln. with FeCl, and pptd. with ZnCl, Orancg basic mordant dye. 

S. 603 and 604.—‘‘Acridin Orange.” 


516,577—Mar. 13, 1894. Erhart SCHLEICHER, Germany. (DPadische.) 
Basic yellow dye. Diamino phenyl acridin carbo acid, ethyl ester. 

FLUORESCEIN is treated with NH, so as to obtain a diamino acripiIn and product then re- 
fluxed in ninety-five per cent alcohol through which a stream of HCl gas is passed. Closed 
vessels under pressure and other alcohols and acids may be used for the esterification. YELLOW to 
ORANGK basic mordant leather dye. 


$37,723—Apr. 16, 1895. Jakob Scumip and Karl Jepuicxa, Switzerland. (Basle.) 
Orange dye. Alkylated dyes of acridin group. 


ACRIDIN YELLOW, benzoflavin or other, together with methyl alc. and HCl, or other, heated 
in closed vessel to 160-200°. YELLOW to ORANGE basic mordant dyes, for leather, etc. 
S. 603—‘‘Acridin Orange;’’ also 604, 605, etc. 


_ 546,177—Sept. 10, 1895. Carl Mutier, Germany. (Badische.) 
Brown-yellow dye. Product like Phosphine in properties. 

Tetra methyl diamino BENZOPHENONE condensed with 3-PHENYLENE DIAMIN HCI and 3- 
PHENYLENE DIAMIN by heating with ZnCl, in closed enameled vessel, on oil bath to 195-215°. 


The 3-amino phenyl auRAMIN first formed combines with diamin to form the new dye. 
S. 607—‘‘Rheonin A.” 


617,340—Jan. 10, 1899. Paul Jutius and Georges E. DarirEr, Switzerland. (Badische.) 
Phosphin dye and process of making same. as-Diphenyl dimethyl triamino phenyl 

ditolyl acridin. 

Dimethyl 4-amino BENZALDEHYDE heated at 140-150° with phenyl 3-TOLUYLENE DIAMIN. 
YxLLow basic mordant dye, for leather, etc. 

Note 619,577. 


619,577—Feb. 14, 1899. Paul Jutius and Akim Txatscu, Germany. (Badische.) 
Process of making yellow phosphin dye. Diphenyl triamino phenyl! ditolyl acridin. 


Phenyl 3-TOLUYLENE DIAMIN or homologs condensed by boiling with 4-amino BENZALDEHYDE 
or homologs, in presence of FeCl,. preferably in alc. soln. Completely oxidized dye thus ob- 
tained in larger yield and greater purity because by-reactions are avoided. YELLOW basic mor- 
dant dye, for leather. 

Addition to 617,340. 


2 DIGEST OF PATENTS 


637,183—Nov. 14, 1899. Henry TerrissE and Georges Daritr, Switzerland. (Badische.) 
Yellow basic dye. 2-Amino 3-methyl phenyl 1.2-naphth acridin. 


2-NAPHTHYLAMIN is heated to 150° and to this is added a mixture of 2.4-diamino 5-methyl 
ToLUYL alcohol and 2-NAPHTHYLAMIN HCl then temp. raised to 170°, diluted, filt. hot, 
cooled, filt. to remove naphthylamin HCl, and base pptd. by alk. YxrtLow basic mordant dye, 
for leather. 


643,569—Feb. 13, 1900. Fritz ULLMANN, Germany. (Berlin.) 


Yellow acridinium dye. Acridin dyes substituted in N position to form acridinium salts 
containing pentavalent nitrogen. 


Amino tolu napth AcRIDIN, two parts in boiling nitrobenzene soln., to which one part of 
DIMETHYL sulfate is added. Other components claimed. Orange-yELLOW basic mordant dye, 
fast to alk. carbonates. 


644,324—Feb. 27, 1900. Paul Jutius and Walther Reiss, Germany. (Badische.) 
Process of making yellow basic dyes. Probably an amino tolu naphth-acridin. 


Diamino TOLUYL ALCOHOL, derived from 3-TOLUYLENE DIAMIN and FORMALDEHYDE, mixed with 
cryst. FeCl,, added to molten 2-NAPHTHOL at 140° then heated to 150-170°. YELLOW basic 
mordant dye. 


666,095—Jan. 15, rgo1. Carl Jepuicxa, Switzerland. (Basle.) 
Orange dye and process of making same. Alkylated diamino ditolyl acridinium derivs. 
or other. 


PATENT PHOSPHIN G derived from ACRIDIN YELLOW and METHYL sulfate ‘‘a’’,* heated in 
autoclave at 100—110° with alcohol and METHYL chloride. If an alkyl sulfo acid is used solvent 
should be aq. free (Nitrobenzene, etc.), or diamino ditolyl methyl acridinium ‘‘b’? is heated in 
methyl alcohol-sulfuric acid at 160-170°. Other components claimed. 

*For alkylation in amino groups “a” or in N of nucleus “b” see 537,723 and 666,096. 


666,096—Jan. 15, 1901. Karl JEDLICKA, Switzerland. (Basle.) 
Yellow acridin dye and process of making same. Diamino ditolyl N-ethyl acri- 
dinium. 


ACRIDIN YELLOW, alkylated by ErHy1 chloride, or other as in 537,723 to PATENT PHOSPHIN 
Gc. is then heated in alk. carb. or NH, soln. YELLOW to orange-YELLOW basic mordant dyes, 
fast to alk. 


675,568—June 4, 1901. Oscar NastvocGELt, Germany. (Elberfeld.) 
Yellow acridin dye and process of making same. Phenyl tolyl acridin. 


Dimethyl diamino puENnyL tolyl methane, dinitrated (ortho), reduced to diamino compound, 
condensed and oxidized. YELLOW basic mordant dye. 
Near S. 60z2—‘“‘Acridin Yellow.” 


709,187—Sept. 16, 1902. Arthur WEINBERG, Germany. (Cassella.) 
Yellow acridin dye and process of making same. 


Tetra amino pITOLYL methane heated at 145-150° with dil. HCl in autoclave, cooled, one 
mol. each of ANILIN and FORMALDEHYDE added and again heated at 105—110° in autoclave. Jeuco 
dye oxidizes in air. Alphyl, alcoyl, and leuco derivs. as well as other aromatic .amins are 
claimed. Orange-rREpD basic mordant fast dyes. 


712,421—Oct. 28, 1902. Otto Soust, Germany. (Ho6chst.) 


Yellow to red acridin dye and process of making same. Tetra alkyl diamino 
benzyl acridinium or other. 


ACRIDIN YELLOW base or homologs, heated with BENZyL chloride in nitrobenzene as solvent 
or in slightly moist condition. YELLOW to RED basic mordant dyes, fast to sodium carbonate and 
NH,. 
716,084—Dec. 16, 1902. Oscar NastvocEeL, Germany. (Elberfeld.) 
Yellow acridin dye and process of making same. Formate of acridin base. 


_ AcrIpDIN base or benzoflavin base, in dil. soln. of ForMIc acid or other mono basic fatty 
acid, evaporated to dryness at 100°. Green YELLOW basic mordant dyes. 


GROUP I.—ACRIDIN 3 


716,264—Dec. 16, 1902. Carl L. MuuiEer and Ernst Scumip, Germany. (Badische.) 
Acridin dye. 
Phthalyl 3-roLUYLENE DIAMIN, or phthalic anhyd. together with 3-ToLUYLENE DIAMIN and 


its HCl salt, heated in enameled vessel to z00-210° with ZnCl, YELLOW to orange-RED basic 
mordant dye. 


730-771—June 9, 1903. Karl Jepuicxa, Switzerland. (Basle.) 

Yellow acridin dye and process of making same. Diamino dimethyl! acridin. 
3-TOLUYLENE DIAMIN and FORMALDEHYDE, acetic aldehyde, or other, heated in dil. HCl soln. 

at 130-140° in an autoclave, cooled and with ACETALDEHYDE heated at 80-90° in aq., pptd. as 


ZnCl, double salt. YELLOW to ORANGE basic mordant dyes, easily soluble. 
S. 60z2—“‘Acridin Yellow.” 


739,117—Sept. 15, 1903. Otto Soust, Germany. (Hoéchst.) 
Yellow acridinium dye and process of making same. Acridinium dyestuffs, alky- 
lated at the acridin N and in amino groups. 


3-TOLUYLENE DIAMIN or other in strong HCl soln., FoRMALDEHYDE added and equiv. amount 
of ACETALDEHYDE, or other, slowly added at common temp., soln. then heated with more HCl 
in closed vessel to 140°, cooled, METHYL alcohol added and heated to 170°, finally oxidized by 
air and FeCl,. More methyl alcohol and higher temp. gives redder and ethyl alcohol a yellower 
product. YELLOW basic mordant dye. 

Near S. 602—“‘Acridin Yellow.’? Note related pats. 666095 and 96. 


740,468—Oct. 6, 1903. Christopher Ris and Albert Myzius, Switzerland. (Geigy.) 
Acridin dye and process of making same. 


Diformyl 3-TOLUYLENE DIAMIN and 3-TOLUYLENE DIAMIN, heated with anILIN HCl gradually 
to 160° till maximum color develops. Other components claimed. YELLOW to ORANGE and BROWN 
basic mordant fast dyes. 


746,981—Dec. 15, 1903. Carl L. MuLuerR, Germany. (Badische.) 
Acridin dye and process of making same. 


ACRIDIN YELLOW with two parts GLYCERIN heated to 170—-180°, diluted, pptd. with NaCl and 
HCI salt formed. Other acridin dye-glycerin comps. claimed. ORANGE to YELLOW basic mordant 
dyes. 


766,540—Aug. 2, 1904. Otto Soust, Germany. (Héchst.) 
Orange dye and process of making same. Alkylated glycin acridin. 


3-TOLUYLENE DIAMIN condensed with FORMALDEHYDE in HCl soln. to form leuco acridin, then 
with CHLORACETIC acid to form leuco glycin acridin, alkylated and finally oxidized. ORancxr to 
RED basic mordant dyes. 


794,052—July 4, 1905. Otto Soust, Germany. (Hoéchst.) 
Orange-red acridin dye. (Process also claimed.) 


ACRIDIN YELLOW, or leuco dye, salt or base, alkylated with HCl and atconon then product 
heated in dil. H,SO, with FoRMALDEHYDE. Dye pptd. as Zn salt. Orange-rEpD basic mordant 
dye. 


1,005,176—Oct. 10, 1911. Paul Enriicu and Louis Benpa, Germany. (Cassella, N. Y.) 
3.6-Diaminoacridinium and its salts. 3.6-Diamino N-alkyl acridin and salts. 
3.6-Diamino acRIDIN is diacetylated, separated as NH, salt, heated to 180° in 10 parts 


nitrobenzol and one mol. ToLUENE 4-sulfo, methyl ester, added, crystals separated and saponified 
in HCl at 110°. YELLOW to ORANGE basic mordant dye, fast to soda and soaping. 


1,255,739—Feb. 5, 1918. Heinrich GRUNHAGEN, Germany. (Berlin.) 
Halogenated dye of the acridin series. (Process also claimed.) Halogen as-dialkyl 
diamino acridin. 
2-Amino formyl 4-amino CHLORBENZENE melted together with 3-amino dimethyl ANILIN at 
180°, diluted, filt. and pptd. by NaCl or ZnCl,. Process is essentially the same as that em- 
ployed in 1889 by Bender. (S. 602). Orange-yELLow basic mordant dye. : 
Near S. 602—“‘Acridin Yellow G.” Note addition pat. 1,226,740. 


4 | DIGEST OF PATENTS 


1,255,740—Feb. 5s, 1918. Heinrich Grunuacen, Germany. (Berlin.) 
Dyes of the benzene-naphthalene series and process for their manufacture. 

Naphthyl dialkyl amino acridin. 

Formyl 2-NAPHTHYLAMIN, or other, melted together with 3-amino dimethyl an1zr1n HCl, or 
other, to 160-190°. ORANGE to orange-YELLOW basic mordant dyes. 

Addition to 1,285,739. 


1,418,852—June 6, 1922. Charles VAUCKER and Rene SpEITEL, Switzerland. (Durand.) 
Halogen derivatives of basic acridine dyestuffs and process of making same. 
Acridin dyes with more than one atom halogen in molecule. 
ACRIDIN ORANGE sulfate (tetramethyl 2.7-diamino acripIN disulfate) mixed with NaBr added 
to 8 parts conc. H,SO, at 0° for several hours then heated at 50° till sol. in aq. with red color. 
Br vapor in nitrobenzene soln. aided by NaClO,, or excess Br alone may be used. Red basic 


mordant dyes. 
Note 1,255,739 for halogen acridin dyes by another process. 


1,427,431—Aug. 29, 10922. Louis Benpa, Germany. (Cassella.) 
Compound of the acridine series and a process of making same. Acridin dyes 

condensed with formaldehyde. 

3.6-Diamino N-methyl acripiIn HCl, homologs or analogs, in dil. HCl condensed with 
FORMALDEHYDE at usual temp. Amount of formaldehyde may vary greatly. YELLOW basic mor- 
dant dyes, useful also for medicinal purposes. 

Note 1,427,432 among applications. 


1,427,432—Aug. 29, 1922. Louis Benpa, Germany. (Cassella.) 
Acridinium compounds and a process of making the same. Tannin lakes of 

acridin dyes. 

3-6-Diamino N-methyl acriptn HCl*, homologs, etc., in aq. soln. mixed with 2 parts 
TANNIC acid containing sod. acetate. Compounds are suitable for lake colors and for medicinal 
comp. 

*T rypaflavin.” 


1,455,486—May 15, 1923. Heinrich Grinuacen, Germany. (Chem. Found.) 
Dyes of the acridine series and their manufacture. as-Dimethyl 2.7-diamino 3.6- 
dimethyl acridin, or other. 

Formyl 4.3-TOLUYLENE DIAMIN and equimol. 3-amino dimethyl ANILIN are heated at 185- 
190° with or without a diluting agent such as glycerin or naphthalene until no more H,O is 
evolved (about 6 hours). Homologs and diformyl derivs. of toluylene diamin may be used. 
Yellow-brown powds., sol. in aq.; YELLOW to orange-RED to BROWN basic mordant dyes for leather. 

Near S. 602 or 603—‘‘Acridin Yellow” or “‘Acridin Orange.”’ 


1,455,487—May 15, 1923. Heinrich GriNHAGEN, Germany. (Chem. Found.) 
Dyes of the acridine series and process for their manufacture. Ethyl dimethyl 
2.7-diamino 3.6-dimethyl acridin. 
Process is same as 1,455,486 except that both amino groups are substituted by alkyl. Red- 


brown powds.;.yELLOwW basic mordant dyes for leather. 
Near S. 602—‘“‘Acridin Yellow.” 


1,455,488—Sept. 10, 1923. Heinrich Griinnacen, Germany. (Chem. Found.) 
Dyes of benzene-naphthalene-acridine series and their manufacture. 2-Amino 
3-methyl phen naphthacridin. 
Process is similar to 1,455,486, except that one of the components is 2-NAPHTHYLAMIN Of 


deriv. 


1,473,550—Nov. 6, 1923. Heinrich GriinHacen, Germany. (Berlin.) 
2.7-dialkyl-3-dialkylamino-6-amino-10-alkylacridinium salts. 


One part 2.7-dimethyl dimethyl 3-amino 6-amino AcRIpDIN suspended in 2.5 parts methyl alc. 
with a soln. of 0.47 parts METHYL bromide or other alkyl halogen in 1 part methyl alc. is heated 
in an autoclave for 6 hours at 130°. Alcohol is removed by distn., boiling aq. soln. of product 
made weakly alk. with Na,CO, and pptd. by salt. Heated with excess NaOH the acridinium 
base is sepd., and HCl salt may then be formed. YELLOW basic dyes. 


GROUP II.—ANILIN BLACK 5 


Group I1—ANILIN BLACK. 


38,589—May 109, 1863. Re. 4,746—Feb. 6, 1872. Div. A. John Licurroot, England. (Pack.) 


Improvement in dyeing and printing textile fabrics and yarns with anilin 
black. 


ANILIN is oxidised by KC1O,, perchloride of copper, NH,Cl, etc. Methods for dyeing and 
printing are given. A BLAcK developed dye that resists chemical reagents. 

S. 922—“‘Anilin Black.” Note also 79,942 (Benoit Bloch) in which arsenic acid is used as 
oxidizing agent; 96,242 (Charles Lauth) in which permanganate salts are used; 111,654 which 
employs chromates, chlorates, copper, iron, uranium, or vanadium salts; and 193,158 (W. J. S. 
Grawitz), which employs sesquioxide of iron, chromates, or chlorates. 


38,589—May 10, 1863. Re. 4,747—Feb. 6, 1872. Div. B. John Licurroot, England. (Pack.) 
Improvement in fabries dyed with anilin black. 

ANILIN in HCl soln. added to soln. of KCI1O,, acetic acid, perchloride of Cu, and NH,Cl 
etc. Fabric or yarn is steeped in this solution, wrung out, dried, steamed, or aged at 10-20°, 


then passed through alk. aq. Printing process described and other components claimed. 
S. 922—‘“‘Anilin Black.” 


79,942—July 14, 1868. Re. 3,103—Sept. 1, 1868. Benoit Biocu, France. 
Improved anilin dye. 


ANILIN on fiber oxidised by arsenic acid. Used in dilute solution, gray is produced in- 
stead of black. Gray to sLAcKk developed dyes. 
S. 922—“‘Anilin Black.” 


96,242—Oct. 26, 1860. Charles Lautu, France. 
Improved coloring-material for dyeing and printing. (Process, not product, 
claimed.) 


ANILIN, toluidin, cumidin, napthylamin, etc., and an oxidising agent, preferably per- 
manganic salts, applied and developed on fiber as dye or print. Buiacx developed dyes. 
S. 922—“‘Anilin Black.” 


111,654—Feb. 7, 1871. (See Re. 7,429-7,432.) John LicutTrFoor, England. 
Improvement in dyeing and printing textile fabries. 


ANILIN, oxidised in printing paste or on fiber using chlorates, copper salts, chromates, iron, 
uranium or vanadium salts. A BLACK developed dye. Method of producing cream of tartar 
by double decomp. of sod. or ammonium acid tartrate and KCIO, is also claimed. 

Re. 7,429—Dec. 12, 1876.—-Division A claims use of chlorate of soda as oxidizer with sol. 
salts, oxides, sulfides or finely divided metallic Fe as catalysts. 

Re. 7,430—Dec. 12. 1876.—Division B claims chlorate of ammonia as oxidizer, also with 
sol. salts, oxides sulfides or finely divided metallic Fe, as catalyst. 

Re. 7,431—Dec. 12, 1876.—Division C claims use of an alkaline chlorate as oxidizer with 
vanadium, its salts, oxides or sulfides as catalyst. 

Re. 7,432—Dec. 12, 1876.—Division D claims use of an alkaline chlorate as oxidizer with 
uranium, its salts, oxides or sulfides as catalyst. 

S. 922—‘“‘Anilin Black.” 


134,076—Dec. 17, 1872. Francois Lamy, France. 
Improvement in dyeing fabrics with naphthylamine colors. 
NAPTHYLAMIN and derivs. oxidised by chloric, chromic and hydrofluosilicic acids, iron or 


copper salts and further treated with chlorine or ammonia, etc., to develop brown violet shade. 
Rep to vioLEt developed dyes suitable for printing, equal to madder dyes. 


138,155—Apr. 22, 1873. James Hiccin, England. 


Improvement in dyeing with aniline black. Use of disulfocyanide of copper as an 
assistant oxidizer, with anilin HCl free of excess acid. 


AniuIn base, com’l., 100 parts mixed with soln. of 250-280 parts of iron sesquichloride or 
400-450 parts chromium sesquichloride (50° Tw.). For printing pastes, this is compounded with 
copper disulfocyanide paste made by mixing 2 parts cryst. CuSO, and 3 parts cryst. FeSO, in 
aq. soln. and adding KSCN. ; 

S. 922—“Anilin Black.” 


6 DIGEST OF PATENTS 


189,538—Apr. 10, 1877. Justus WouFr and Ralph Betiey, England. 
Improvement in production of coloring matters from aniline. 


ANILIN, with or without toluidin or xylidin, oxidized with nitro benzene or nitro toluene 
by heating gently with SnCl, crysts. then raising temp. to 200-220° until sol. in aq. with brown 
yellow color. Instead of SnCl, may be used either HCl or arsenic acid, Cl gas, Br, I, MnO,, 
PbO,, HNO,, or nitrate, chloric, bromic, or iodic acids, with oxygen, metallic perchlorides, 
CuSO,, etc. Gray to BLack developed dyes. 

S. 922—“‘Anilin Black.” 


193,158—July 17, 1877. William J. S. Grawitz, France. 


Improvement in dyeing yarns and fabrics in anilin-black. Process for apply- 
ing anilin black or gray to cotton, flax, wool, silk, feather, etc. 


ANILIN oxidised by perchloride of iron and chromates or chlorates, manganates, permanga- 
nates, tungstates, vanadates, bivanadates, uranates, ferricyanides and cerium, nickel, cobalt, etc., 
comps. of metals whose salts are readily converted to lower degrees of oxidation. Gray to 
BLACK developed dyes. 

S. 922—‘‘Anilin Black.” 


298,998—May 20, 1884. Prosper Monnet, France. (Monnet.) 
Obtaining brown dyes from the aromatic diamines. 


4-PHENYLENE DIAMIN HCI, or other, in dil. H,SO, soln. thoroughly impregnated on fiber which 
is wrung out and oxidized in bath containing KClO, and salt of vanadium for slow action, or 
bichromate to develop more rapidly. Fabric may be immersed more than once and may be 
mordanted; cotton must be mordanted with sumac for deep shades. Brown developed dyes. 
S. 923—‘‘Ursol D.” Schulz credits patent to E. Erdmann, 1888. 


355,934—Jan. 11, 1887. Thomas Hoturpay, England. 
Dyeing textile animal fibers. Dyeing animal fibers with product of oxidization of 
napthol. 


Fiber steeped in dil. H,SO, soln. of bichromate washed and dyed in 1-NapPtHorn soln. with 
or without other colors such as Indigo extract to obtain mixed shades. Shade varied by 
quantity of material. Brown to BLAck developed dyes (not claimed). 


387,097—July 31, 1888. Prosper Monnet, France. 
Dyeing colors by the simultaneous oxidation of diamines and monamines. 

(a) 4-PHENYLENE DIAMIN HCl and anizt1in HCl in molecular proportions. (b) Sodium 
chlorate, and ammonium vanadate in HCl soln., largely diluted. Fiber is dipped in mixture of 


equal vols. of (a) and (b) then aged in air. Briacx developed dyes. 
S. 922—“‘Anilin Black.” 


681,613—Aug. 27, 1901. René Boun, Germany. (Badische.) 


Process of dyeing. Dyeing with tetroxy naphthalene. 


Wool fiber is treated in dil. acetic bath with tetroxy NAPHTHALENE, bichromate added to 
bath, which is further heated for three-fourths hour. Methods for dyeing silk and cotton given. 
Brown to BLACK acid mordant (Al) or developed (CrO,) dyes. 


739,071—Sept. 15, 1903. Emile A. Fournraux, New York. (Metz.) 
Process of dyeing brown. 


Fabric padded or printed with soln. containing 3-TOLUYLENE DIAMIN, or other, with acid 
(preferably mineral), gum, tragacanth, NaClO,, AICI, and a little cerium or copper chloride as 
catalyzer (or mixture of these) steamed or aged as usual. Product differs from diamin browns. 
Brown developed dye, suitable for printing. 


787,221—Apr. 11, 1905. Alexander S. Ramacg, Michigan. 
Electrolytic method. Electrolytic mfr. of anilin black. 


An aq. soln. of a metallic salt is electrolyzed with an insoluble anode, cathode product is 
recovered, and an ANILIN comp. oxidized at the anode to anilin black, which is separated and 
acid anode liquor again used. Sod. sulfate with lead anodes, NaCl with graphite anodes and 
FeSO,, etc., using H,SO, or HCl and corresponding anilin salt are claimed. 

S. 922—“Anilin black.” 


GROUP II.—ANILIN BLACK 7 


796,715—Aug. 8, 1905. Victor Fusscancer, Germany. (Hochst.) 
Process of dyeing violet to black. (Product also claimed.) 


4-Amino DIPHENYLAMIN or its derivs. jointly oxidized on the fiber with rEsorcin, or other 
phenol or amin, one mol. each, by applying the two together with a chlorate or other oxidizing 
agent and various assistants to the fiber, drying, developing, fixing, etc., by heat or steam. 
BLUE, VIOLET to BLACK developed dyes fast to alks. acid, light, and organic solvents. 


800,735—Oct. 3, 1905. Hugo GELDERMANN, Germany. (Berlin.) 
Diamidodiphenylamin sulfonic acid and process of making same. 


4-Methyl 3-amino 4’-nitro DIPHENYLAMIN 2-sulfo derived from 4-nitro CHLORBENZENE-2-sulfo 
and 3-PHENYLENEDIAMIN, boiled in dil. HCl with Zn powd., soln. made alk., filt., made slightly 
acid with HCl and pptd. by salt. Buur developed dye when oxidized on fiber. (Not claimed.) 


863,761—<Aug. 20, 1907. Henri Scumip, Germany. (Badische.) 
Production of brown shades on the fiber. 


4-PHENYLENE DIAMIN, homolog or isomer, is dyed or printed on the fiber by compounding 
with the usual oxidizer such as a chlorate and a little Rongalite C, or bisulfite or other reducing 
agent, some NH,Cl, glycerin, tartar emetic soln. and just before use with ammonium vanadate. 
Use of each ingredient is explained and variations in procedure given. A BRowN developed 
dye. 


923,635—June 1, 1909. Ernst ErpMann, Germany. (Berlin.) 
Hair-dye. 

2-Amino PHENOL 4-sulfo, 4 parts, combined with 1.6 parts Na,CO, to form sodium salt, and 
applied to hair or other fiber in admixture with an oxidizing agent and a small proportion of a 
bisulfite. Other amino sulfo acids of benzene series claimed. Light to dark BROWN and BLACK 
developed dyes, especially adapted to dyeing of human hair. 


992,947—May 23, Io11. Arnold ErRtENBACH, Germany. (Berlin.) 


Process of dyeing hairs, furs, and the like. Dyeing anilin black that will not become 
red-brown in storage. 
4-PHENYLENE DIAMIN is mixed with 2.4-diamino ANISOL, or homolog, and an oxidizing agent 
like H,O,. Use of anisol, etc., instead of usual 3-PHENYLENE DIAMIN stabilizes the blue black 


tone of dyeing. A sracx developed dye. 
S. 922—‘“‘Anilin Black.” 


1,105,447—July 28, 1914. Karl Marx, Germany. (Berlin.) 
Process for dyeing furs, hairs, and the like. 


Nitro 3-diamino ANisoL obtained by nitrating diacetyl 3-diamino anisol, together with H,O, 
or chromate, or other oxidizer, is dyed by usual process on fur that may or may not be pre- 
viously mordanted. Other nitro meta diamino derivs. are claimed. RED, YELLOW to green 
BROWN developed dyes, fast to light and weather. 


1,105,501—Jnly 28, 1914. Arnold ErLtenBAcH and Karl Marx, Germany. (Berlin.) 
Dyes for dyeing furs, hairs and the like. 


4-Amino dimethyl ANILIN, or other asymmetric mono or dialkyl deriv. of a para diamin, 
mixed with one half part 2.4-diamino ANISOL or analogous comp. is dyed on fur that may or may 
not have previously been mordanted with FeSO, Briacx developed dyes for furs, hair, etc. 
Note 992,947 for patent using iron alkyl derivs. 


1,105,554—July 28, 1914. Arnold EruensBacu, Germany. (Berlin.) 
Preparation for dyeing hairs, furs, and the like. 

4-PHENYLENE DIAMIN, two mols, and one mol 2.4-diamino ANISOL (4-amino ANISIBIN) 
thoroughly mixed and ground, or melted together, dissolved in 180 parts aq. and 20 parts H,O, 
added for dyebath. Blue siacx developed dye. 

Near S. 923—‘“‘Ursol D.”? Note addition pats. 1,144.181 and 1,144,325. 
1,326,367—Dec. 30, 1919. Julius A. Nreuwianp, Indiana. 


Dye and process of dyeing. Anilin Black dyeings with mercury salts as catalyzers. 


4-PHENYLENE DIAMIN one mol. in aq. or dil. alc. soln. mixed with one mol. salt of mercury,- 
preferably the acetate, heated to boil and fiber added. Or fiber may be separately immersed, 


8 DIGEST OF PATENTS 


first in mercuric acetate soln. then in boiling dil. alc. soln. of diamin, preferably after dipping 
in soln. of Zn Cl, or NaCl. Excess Hg salt ppts. dye in soln. Buackx developed dye. 
S. 922—“Anilin Black.’’ 


1,416,646—May 16, 1922. Oskar KaLtwassER and Hans Orurn, Germany. (Berlin.) 
Process for dyeing skins, hairs, and the like. 
5-Nitro 2-amino PHENOL together with NH,OH and H,O,, dyed at common temp. on skin, 


hairs, etc., that have previously been mordanted with Fe, Cr or Cu. YELLOW (Fe) to BROWN 
(Cr.Cu.) acid mordant and developed dyes, fast to light. 


Group III.—ANTHRAQUINONE. 


95,465—Oct. 5, 1869. Re. 4,320—Apr. 4, 1871. 
Charles GraEBE and Charles LirsERMANN, Germany. 

Improvement in the manufacture of alizarine. 1.2-Dihydroxy anthraquinone. 

ANTHRACENE (a) oxidized by K,Cr,O, or HNO, in acetic soln. to form ANTHRAQUINONE, then 
heated with Br or Cl to dibrom product, or (b) tetrabrom ANTHRACENE formed then heated with 
HNO,, and product of (a) or (b) heated in dil. alk. 

Re. 4,321—April 4, 1871. Product patent for Re. 4,320. For sulfo deriv., see S. 780— 
Alizarin Red S. 

S. 778—“‘Alizarin V.” 


97,597—Dec. 7, 1869. Re. 4,558—Sept. 19, 1871. 
Julius BronNNER and Hermann Gutzkow, Germany. 
Impovement in preparing coloring matters from anthracene. Dioxy anthraqui- 
none or alizarin, and purpurin. 


ANTHRACENE derived from asphaltos or pitch is oxidized with HNO, or bichromate and sul- 
furic to ANTHRAQUINONE, dinitrated by mixed acids, washed and then heated in conc. caustic 
alk. to 220°. Process differs from Graebe and Liebermann or Caro’s because first nitrated, not 
sulfonated, while second part of both processes uses alkaline fusion to convert into hydroxyl 


deriv. 
S. 778—“Alizarin V.” 


127,426—June 4, 1872. William H. Perkin, England. 
Improvement in the manufacture of coloring matters from anthracene. 
‘Dioxy anthraquinone from anthracene. 
ANTHRACENE purified and chlorinated or brominated by exposure in thin layers to halogen 
vapors, or by treating benzene soln. of anthracene with halogen vapor, sulfonated at 130-150°, 
oxidized in sulfuric soln. with MnO, or by heating strongly in sulfuric acid, then fused in 


caustic alkali, or other. 
S. 778—“‘Alizarin V.” 


153,536—July 28, 1874. Heinrich Caro, Charles GragBE and Charles LigBERMANN, Germany. 
Improvement in the preparation of coloring matters from anthracene. 

Dioxy anthraquinone. 

ANTHRACENE Or ANTHRAQUINONE, sulfonated in H,SO, (1.848) at 100-150°, oxidized in same 
soln. after dilution with MnO, or other strong oxidizing agent, the alkali salts of anthraquinone 
sulfo acids separated and fused in 2-3 parts caustic alkali at 180—260°. 

S. 778—“‘Alizarin V.”’ 


154,153—Aug. 18, 1874. 
Carl Rumprr, New York, Friedrich Bayrr, Friedrich WeEskort, August SILLER, Germany. 
Improvement in treating anthracene and the manufacture of dyes. Dioxy 
anthraquinone. | 
ANTHRACENE purified by pressing out oily matters and crystallizing from benzene, alcohol 
(ninety per cent pure), etc., is oxidized by heating dry with 1-5 parts MnO, in closed vessel to 
200° and resulting ANTHRAQUINONE, sulfonated in fuming acid, and fused in alkali by usual 


processes. 
S. 778—“‘Alizarin V.’’ 


GROUP III.—ANTHRAQUINONE 8) 


186,032—Jan. 9, 1877. Heinrich Caro, Germany, 


Improvement in obtaining coloring matters suitable for dyeing and print- 
ing. 1.2-Dioxy 3-nitro anthraquinone and 1.2.4-trihydroxy anthraquinone. 


ALIZARIN (pure or com’l) dry or dissolved in suitable solvent, acted upon by nitrous or 
byponitrous acids to produce alizarin orange which is heated in conc. sulfuric soln. to form 
compound like purpurin. Several methods of mfr. and of purification are given in detail. 
ORANGE, RED to red BROWN vat dyes. 

S. 779, 783 and 803—“‘Alizarin Orange,” “‘Alizarin Blue” and “Purpurin.” 


188,061—Mar. 6, 1877. Felix De LaLanng, France, 


Improvement in process of obtaining artificial purpurine from alizarine. 

Purpurin from alizarin. 

ALIzaRIN heated at 200-220° in 10 parts 66° sulfuric acid, containing 0.5 to 1 part anti- 
monic acid till test drop with dil. NaOH gives currant red color, then diluted in 20-30 vols. aq. 
boiled, filt., washed, etc. REp to Brown (Cr) acid mordant dyes. 

S. 783—‘“‘Purpurin.” 


188,217—Mar. 6, 1877. Justus WouFF and Ralph Betiey, England. 


Improvement in processes of making dyes from naphthaline. Alizarin and 
derivs. (probably). 

NAPHTHALENE and dichlor benzene, 1 mol. each, heated in autoclave with two mols. Zn 
powd. at 220° until aq. sol., dissolved in glac. acetic acid and while warm CrO, or other 
strong oxidizing agent is slowly added until action ceases. Product is separated and sulfonated 
in 3-4 parts fuming sulf. at 220-230°, converted to the Ca deriv. and finally heated with NaOH 
at 170-200°, until completely pptd. by acid. 


258,530—May-. 23, 1882. Heinrich Bruncx, Germany. (Badische.) 
Manufacture of anthracene-blue. Bisulfite compound of alizarin quinolin, or 1.2-dioxy 
anthraquinolin. : 


ALIZARIN, purified, treated with nitrous, or other, acid to form Alizarin Orange, then 1 part 
fifteen per cent paste heated with 1 part glycerin and 5 parts 66° sulfuric acid to 100°, product 
separated and treated with bisulfite to form “Anthracene Blue.’”’ <A cryst. mass, easily sol. aq. 
(RBr), decomp. above 70° by strong acids or alks. or carbonates, reproducing the original dye, 
not decomp. by organic acids or their salts, the advantage of which is shown in 274,081. A 
BLUE acid mordant dye that can be developed on the fiber. 

S. 804—‘“‘Alizarin Blue S.” 


348,613—Sept. 7, 1886. Rene Bown, Germany. (Badische.) 


Manufacture of yellow coloring-matter or dye-stuff from gallic acid. (Prod- 
uct, not process, claimed). Galloflavin. 

Gauuic acid in forty-five per cent alcoholic KOH, oxidized below 10° by agitation or pass- 
ing current of air through till all is pptd., avoiding excessive oxidation, separated by filtration, 
pressed, dissolved in warm aq., 50°, pptd. by HCl or H,SO, and boiled to make ppt. crystalline. 
A pale cryst. powd., of silky luster, sparingly sol. hot aq., in cone. H,SO, (YB), easily sol. 
dil. caustic and carb. alk., forms GREEN to YELLOW lakes or is GREEN to YELLOW mordant dye (AI, 
Cr, Sn mordants) fast to soap, light and air. 

S. 772—“‘Galloflavin W.” 


368,054—Aug. 9, 1887. Rene Boun, Germany. (Badische.) 
Manufacture of soluble naphthazarin. (Product, not process, claimed.) Bisulfite 
comp. of 1.2-dioxy naphthoquinone or soluble naphthazarin. 
1.2-Dioxy NAPHTHOQUINONE digested at 50-70° in closed vessels with strong soln. bisulfite. 
Product resists strong acids, but is easily decomposed by alkalies, forming original comp. The 
ak. soln. has brown color with strong blue-green fluorescence, and dyes BLACK, GRAY, Or SLATE 


colors on acid mordants. 
S. 774—‘“‘Alizarin Black WR, etc.” 


399,479—Mar. 12, 1889. Rene Boun, Germany. (Badische.) 
Alizarine-green. ‘Tri and tetra oxy anthraquinone quinolin and sulfo acids. 


ALIZARIN BLUE, dry and finely divided, slowly added to 10 parts fuming sulfuric (seventy 
per cent anhyd.) then heated to 50°, 20 parts sulfuric (1.84) added and temp. raised to 120- 
125° for 8 hours. Fine blue gray needle crysts., slightly sol. in boiling aq. and dil. alks., forms 


IO DIGEST OF PATENTS 


salts with alk. carbonates (B), forms green comps. with caustic alk., and soluble bisulfite comps. 
with alk. bisulfite; a GREEN acid mordant dye. 

S. 805 and 808—-“‘Alizarin Green S and X.” Note 399,480 to 82. 
399,480—Mar. 12, 1880. Rene Boun, Germany. (Badische.) 
Alizarine-blue sulpho-acid. Alizarin Blue mono sulfo acid. 


ALIZARIN BLUE heated above 100° in ‘‘Nordhausen acid’’ or heated between 100-130° with 
§ parts fuming sulfuric twenty-three per cent anhyd. or up to 170° with weaker acids, etc. The 
sulfo acid dissolves in much boiling aq. (BG); in dil. alk. (B), with caustic (G), pptd. from 
this soln. as crysts. of free acid by salt or by HCl (V crysts. of free acid) and in excess HCl 
redissolves (R), forms bisulfite comps; a green BLUE acid mordant dye. 

S. 808—“‘Alizarin Green X.” Addition to 399,479. 


399,481—Mar. 12, 1889. Rene Boun, Germany. (Badische.) 
Alizarine-blue sulphurie acid. Sulfonated Alizarin Blue sulfuric acid comp. 


ALIZARIN BLUE, dry, finely powdered, added in small portions to fuming sulfuric (twenty- 
three per cent anhyd.) heated to 50° for 4-5 hours then cooled to common temp. for 12 hours, 
carefully excluding moist air. Easily decomposed by acids, mineral, acetic or CO, Product 
forms two alk. salts,—with little alk. (Y) or (Br), with more alk. (V) or (B); the latter with 
small amount of acid returns to (Y) or (Br), and with more acid ppts. (Y); a BLUE acid mor- 
dant dye, for wool only. 

S. 808—‘“‘Alizarin Green X.’’ Addition to 399,479. 


399,482—Mar. 12, 1880. Rene Boun, Germany. (Badische.) 
Alizarine Indigo-blue. Tetra and penta oxy anthraquinone quinolin sulfo acids. 

ALIZARIN GREEN, dry, powd., or in sulfuric acid soln. as in 399,479, heated in 20 parts 
sulfuric (1,848) at 210° till blue, diluted, filtered, etc., and dried or used as paste. Product is 
insol. in hot aq., forms blue salts with alks., which salts are insol. in caustic alk., sol. conc. 
H,SO, (B) (alizarin green soln. is red), forms sol. bisulfite comps; an indigo BLUE acid mordant 
(Cr) dye. 

S. 809—‘“‘Alizarin Indigo Blue S.”’ 


401,633—Apr. 16, 18809. Rene Boun, Germany. (Badische.) 
Alizarine-blue green. Mixtures of tri and tetra oxy anthraquinone quinolin. 

ALIZARIN BLUE (alizarin-quinolin) added in small portion to 10 parts fuming sulfuric 
(seventy per cent anhyd.) while cooling, then heated at 50°, 20 parts sulfuric acid (1.84) 
added, and heated or let stand till soluble in alk. carb. Purified as bisulfite comp. Product 
sol. in much boiling aq. (dark V), when diluted further (BG), in conc. H,SO, (R), in fuming 
sulf. (BG), in caustic alk. (G), not pptd. by excess; forms bisulfite comps. for printing a 
greener BLUE than Alizarine Blue, a blue GREEN acid mordant (Cr, Ni, Zn) dye. 

S. 808—‘‘Alizarin Green X.’”’ Note 399,479. 


401,635—Apr. 16, 1889. Rene Boun, Germany. (Badische.) 
Alizarine-green sulpho-acid, Alizarin green sulfo acid. 

ALIZARIN GREEN (tetraoxy anthraquinone-quinolin), finely divided, added to 20 parts fuming 
sulfuric, (eight to ten per cent anhyd.) then temp. raised to 130-135° till aq. soluble. Bisulfite 
comps. are used in dyeing and printing. A cryst. powd., aq. soln. (BG), changed to (R) by 
mineral acids, forms salts with alk. carb. (B), and with caustic alk. (G) not pptd. from soln. 
by excess, sol. in conc. H,SO, (Br) in oleum twenty-three per cent (YG); a GREEN acid mordant 
(Cr) dye. : 

S. 808—‘“‘Alizarin Green X.” 


415,08S8—Nov. 12, 1889. Rene Boun, Germany. (Badische.) 
Trioxybenzophenone. 
PYROGALLOL is condensed with equimol. Brnzorc acid at 140° with ZnCl, as condensing 


agent. YELLOW to BROWN acid mordant (Al, Sn, Fe, etc.) dyes, suitable for printing. 
S. 770—“‘Alizarin Yellow A.” 


443,402—Dec. 23, 1890. Marcel V. Nencx1, Switzerland. (Badische.) 
Gallacetophenone. 4.3.2-Trioxy acetophenone or gallacetophenone, m. p. 168°. 


PyROGALLOL heated with glac. acetic acid and ZnCl, at 105°, dissolved in aq. and let stand 
14 hours at 10°. Pale yellow crysts., sol. hot aq., crysts. out on cooling, easily sol. alc., insol. 


GROUP JII.—ANTHRAQUINONE II 


C,H,, sol. in alk. (Yt) which, on oxidation, turns (Br); a YELLOW (Al) or Brown (Cr) acid 
mordant dye. (Not claimed). . 
S. 769—‘“‘Alizarin Yellow C.” . 


446,892—Feb. 24, 1801. Robert E. Scumipt, Germany. ° (Bayer.) 
Alizarine derivative. (Process also claimed.) Principally 1.2.4.5.8-penta oxy anthra- 
quinone. ; 


1.2.5.8-Tetra oxy ANTHRAQUINONE or “Alizarin Bordeaux” in 20 parts 66° sulfuric, to 
which powd. MnO,, or arsenic acid is added and comp. raised to 100°, filt., washed, dissolved in 
hot dil. alk., filt., and pptd. by acid. A brown powd.,’or red brown paste, insol. aq., easily 
sol. alk. (VB), in conc. sulf. (B and fluor) in glac”’ acetic or alc. (OR-VR and YG fluor) 
from which crysts. (YBr needles) are formed; a vioLrET (Al) or green BLUE (Cr) acid mordant 
dye. 

S. 788—“‘Alizarin Cyanin.’? Note 446,893. 


446,893—Feb. 24, 1891. Robert E. Scumipt, Germany. (Bayer.) 
Alizarine derivative. (Process also claimed). 1.2.5.8-Tetra oxy anthraquinone. 


ALIZARIN, Or 1.2-dioxy anthraquinone, ground and highly dried, heated at 35-40° in large 
quantity of sulfuric acid (seventy per cent anhyd.) diluted with ice, filt., and resulting sulfuric 
ester saponified by boiling with NaOH, then pptd. by HCl. An orange red paste insol. aq., 
easily sol. in NaOH and conc. sulf. (BV), crysts. from glac. acetic or benzol (R); a RED (Al) or 
blue vioLtET (Cr) acid mordant dye. 

S. 787—“‘Alizarin Bordeaux.’ Note 446,892 and 476,419. 


450,037—Apr. 7, 1891. Hermann REISENEGGER, Germany. (Hochst.) 
Black dye. Flavopurpurin and anthrapurpurin quinolin. 

Amino FLAVOPURPURIN Or amino anthrapurpurin, from nitro comps. dissolved in 7 parts 
66° sulfuric, 0.5 part each of GLYCERIN and NITROBENZENE added, and heated slowly to 110°. 
Product is purified as bisulfite comp. A black basic dye or paste, sol. in NaOH (VR), sub- 
liming on heating (G needles), heated quickly in tt. with 20 parts Zn dust forms anthraquinolin; 
a GRAY to BLACK acid mordant dye. 


452,210—May 12, 1801. Rene Boun, Germany. (Badische.) 


Process of dyeing with gallacetophenone. Metallic oxide or mordant compound of 
gallacetophenone, dyed or printed on fiber. 


The print color compounded of 37.5 parts dye paste (ten per cent dye), 15 parts Al(SCN), 
(1.15), 7.5 parts of Ca(C,H,O,), (1.075), 7.5 parts acetic acid and 32.5 parts thickening gives 
YELLOW color. To produce yellow Brown prints Cr(SCN), is used instead of Al.comp. and for 
BLACK color iron is used. For dyeing purposes corresponding mordants and assistants. are 
applied in the dye bath. Alumina mordants may be improved by use of Ca and of Turkey red 
oil. Dyeings are usually sensitive to acids, alks. except NH,, and sol. Cr. or Fe salts. 

S. 769—“‘Alizarin Yellow C.” 


476,418—June 7, 1892. Robert E. Scumipt, Germany. (Bayer.) 
Alizarine derivative. (Process also claimed.) Salicylic acid comp. of anthraquinone di- 
quinone. 


ALIZARIN BORDEAUX or 1.2.5.8-tetraoxy ANTHRAQUINONE, as in 446,893, oxidized in 66° sulfuric 
acid, with MnO,°, below 25° to a di-quinone, then an equal weight of SALICYLIC acid added. 
Dye is green black amorph. mass of metallic luster, almost insol. hot aq., sol. Na,CO, (VB), in 
NaOH (GB), pptd. on diln. (YBr); a green BLUE (Cr) acid mordant dye. 

Note 446,892 (S. 788) and 476,419. 


476,419—June 7, 1892. Robert E. Scumipt, Germany. (Bayer.) 
Alizarine dye. (Process also claimed.) Imid of tri or tetra oxy anthraquinone. 

ALIZARIN BORDEAUX OF I.2.5.8-tetra oxy ANTHRAQUINONE, obtained as in 446,893, in 10 parts 
66° sulfuric acid, oxidized by MnO, below 30°, resulting diquinone separated, dissolved in 
twenty per cent NH, and pptd. by acid. A dark violet powd., almost insol. aq.; sol. in alk. 
carb. (RV) in NaOH (B), in NH,OH (BV); in conc. sulf. (dark V); on diln. (R-Br) and 
ppt. (Br); a sLug (Al) or green BLUE (Cr) acid mordant dye. 

S. 7o9—“‘Alizarin Cyanin G.”” Note 446,893 and 476,420. 


12 DIGEST OF PATENTS 


476,420—June 7, 1892. Robert ‘E. Scumipt, Germany. (Bayer.) 
Alizarine derivative. Imid of tetra oxy anthraquinone. 

ALIZARIN BORDEAUX or 1.2.5.8-tetraoxy ANTHRAQUINONE, twenty per cent soln., heated to 80° 
with twenty per cent NH, till red color formed, (when sample is diluted, pptd. by acid and ppt. 
dissolved in conc, sulf.) no longer increases, then the whole is diluted and pptd. by acid. The 
dye, which contains N, forms dark violet crysts., with green reflex, insol. aq., easily sol. 
NaOH (B), in conc. sulf. (R and fluor), pptd. on diln. (YBr). A Brus (Cr) acid mordant dye. 

S. 799 —‘‘Alizarin Cyanin G.” Addition to 476,419. 


476,491—June 7, 1892. Robert E. Scumipt, Germany. (Bayer.) 
Alizarine dye. (Process also claimed.) Imid of salicylic acid comp. of anthradiquinone. 


1.2.5.8-Tetra oxy ANTHRAQUINONE or ALIZARIN BORDEAUX, oxidized in sulfuric soln. with 
MnO, to anthradiquinone which is combined with saticyiic acid, as in 476,418, then heated at 
100° in twenty per cent NH, soln. until when test sample is pptd. by acid, the red violet color 
of the conc. sulf. acid soln. of the ppt. no longer increases. The whole is then diluted and pptd. 
by acid. Dye is olive powd., sparingly sol. aq., easily in Na,CO, (B), in NaOH (GB), in NH, 
or glac. acetic or alc. (VB), in conc. sulf. (RV) pptd. on diln. (RBr); a blue Green (Cr) acid 
mordant dye. 


496,139—Apr. 25, 1893. Robert EK. Scuminpt and Paul Tust, Germany. (Bayer.) 
Alizarin dye. (Process also claimed.) Poly oxy anthraquinone.. 


ANTHRAQUINONE or 1.2.7-trioxy anthraquinone nitrated to b-nitro anthrapurpurin at 20-30° 
by means of HNO, in glac. acetic acid, then oxidized by MnO, in 66° sulfuric acid below 20° 
to OXY ANTHRADIQUINONE, added to large bulk of dil. alk. sulfite soln. and boiled. Boiling with 
aq. or dil. acids or with SO,, etc., is also effective. A brown paste, somewhat sol. boiling aq. 
(Br), easily sol. in acetone, glac. acetic and alc. (BR), in conc. sulf. (RV) on diln. (BV-GB), 
in NH,OH (GB), in alk. carb. (dull V), in caustic (B) pptd. by excess alk.; a dull viotet (Al) 
or green BLUE (Cr) acid mordant dye. 


500,917—July 4, 1893. Isaac Lirpscutitz, Germany. 
Violet-red dye. A sulfonated o-dinitro anthraquinone. 


o-Dinitro ANTHRAQUINONE, sulfonated by heating with 15 parts conc. sulf. at 200°, diluted, 
filtered, ppt. dissolved in boiling KOH, cooled, filtered, and dye pptd. by HCl. Impurities are 
removed by extracting with alc. A dark powd. sol. in hot aq., in alc., C,H, and ether (RV-R 
with Y fluor), gives characteristic absorption spectrum, sol. conc. sulf. (BV with BR fluor), 
in alk. (B), pptd. by acids (B), sublimes (V), may be reduced to anthracene by Zn dust; a 
violet RED acid mordant dye. 


502,603—Aug. 1, 1893. Rene Boun, Germany. (Badische.) 
Green-blue Alizarin dye. 1.3.4.5.7.8-Hexa hydroxy anthraquinones and possibly some 

amino hydroxy deriv. 

1.4-Dinitro ANTHRAQUINONE, heated 1.5-2 hours at 160° with ro parts fuming sulfuric acid 
(twelve per cent SO,), preferably with some sulfur, till easily aq. sol., diluted to monohydrate 
strength and again heated at 130° till insol. in aq. <A dark powd. sol. in alc. (V), insol. in ether 
and C,H,, somewhat sol. boiling aq. (BV), which with alum is (B); a green strug (Cr) acid 
mordant dye. 

S. 789—“Anthracene Blue WR.” S. 800. “Anthracene Blue WG.” Note 389,479-82, 401,- 
633-35, and 519,229. Schulz calls for 1.5-dinitro anthraquinone as material, while patent uses 1.4- 
dinitro deriv. 


502,765—Aug. 8, 18093. Robert E. Scumipt, Germany. (Bayer.) 
Blue alizarin dye. (Process also claimed.) Imid of hexaoxy anthraquinone. 


Hexaoxy ANTHRAQUINONE produced as in 506,265, 2 parts of ten per cent paste, in 20 parts 
aq. and 3 parts.twenty per cent ammonia, treated with current of air or oxygen at atmospheric 
temp., further diluted, boiled and pptd. by acid. A dark paste, insol. in aq:., Sol. in Na,CO, 
(VB), in NH,OH (B), in NaOH (GB), in hot Ba(OH), (B), in glac. acetic or alc. (BR), in 
conc. sulf. (R), pptd. on diln. (Br), gives characteristic absorption spectra; a BLUE (Al) to green 
BLUE (Cr) acid mordant dye. 


GROUP III.—ANTHRAQUINONE r3 


503,295—Aug. 15, 1893. Robert E. Scumipt, Germany. (Bayer.) 
Hexaoxyanthraquinone and process of making it. 1.3.4.5.7.8-Hexa oxyanthra- 
quinone. 


ALIZARIN, quinizarin or any hydroxy deriv., added to 20 parts fuming sulfuric (eighty per 
cent SO,) and kept below 50° for several days until test shows end of reaction, diluted, 
boiled, filt. and ppt. boiled in dil. acid or first in dil. alk. and then pptd. by acid. Product 
crysts. from glac. acetic or C,H,NO, in dark needles, insol. aq., sol. Na,CO,(BR), in NaOH(V), 
pptg. with air (B), in NH,OH(BR), changing in air (V), in conc. sulf. (BV), pptg. on diln. 
(YBr), gives absorption bands; a srug (Cr) acid mordant dye. 

S. 789—“‘Anthracene Blue WR.” Note 446,893 and 502,603 (Bohn). 


506,265—Oct. 10, 1893. Robert E. Scumipt, Germany. (Bayer.) 
Alizarinhexacyanin. (Process also claimed.) Hexaoxy anthraquinone or ‘‘Alizarin hexa- 

cyanin,” different from that of 503,205. 

ALIZARIN BORDEAUX (tetra, tri or penta cyanin) oxidized in sulf. soln. by MnO, or As,O,, or 
at high temps. by H,SO, alone or by other oxidizing agents. ANTHRADIQUINONE is formed as 
an intermediate prod. Dark brown paste insol. in aq., sol. alc. and glac. acetic (R with YBr 
fluor), sol. hot C,H,NO, or C,H,N, in Na,CO,(BV) in NH,OH (BrV-B), in NaOH(GB-V), in 
conc. sulf. (B), which sol. gives absorption spectra, ppts. on diln. (BrR); a vioner (Al) or 
BLUE (Cr) acid mordant dye. 

Near S. 789—‘“‘Anthracene Blue WR.” Note 446,892 and 93. 


511,901—Jan. 2, 1894. Heinrich LausmMann, Germany. (Hochst.) 
Tetranitro-anthrachrysone. (Process also claimed.) Tetra nitro anthrachrysone con- 

taining twelve and one-tenth per cent N (theory twelve and four-tenths per cent.) 

ANTHRACHRYSONE (1.2.5.8-tetroxy anthraquinone), nitrated to tetra nitro compound, by 
pouring its conc. sulf. acid soln. into the calculated quantity of HNO,, then heating to 80°. 
Yellow powd., easily sol. in usual solvents except C,H,, ligroin and CHCl,, pptd from glac. acetic 
soln. by CHCL, as crysts. which detonate at 280-300°, forms alk. salts that also detonate on 
heating; a Brown (Cr) or red Brown (Al) acid mordant dye, fast to fulling. 


519,229—May 1, 1894. Rene Boun, Germany. (Badische.) 
Blue alizarin dye. Hydroxy anthraquinones. 

Mixed dinitro ANTHRAQUINONES obtained as soluble by-product in mfr. of 1.5-dinitro an- 
thraquinone heated with S and fuming sulfuric (forty per cent 50,) at 130° then heated at 130° 
in ninety-five per cent sulfuric till insol. in ag. Dark powd., sol. in alc., almost insol. in ether 
and C,H,, somewhat sol. hot aq. (R), changing with alum to (B), sol. conc. sulf. (VB); a 


BLUE (Cr) acid mordant dye. 
Near S. 789—‘“‘Anthracene Blue WR.” For generic patent see. 502,603; also note 399,479 


to 82, 401,633 to 35. 


527,457—Oct. 16, 1894. Henri N. E. Scuarrer, Massachusetts. 
Soluble alizarin blue. (Process also claimed.) Soluble Alizarin Blue, stable when boiled. 

ALIZARIN BLUE, or other insol. alizarin deriv., rendered anhydrous, heated with 2 parts 
dry cryst. boric acid till fused, cooled, ground, heated, a paste with alkali formed, cooled, again 
ground. Products are sol. in aq., not decomp. by boiling, dye wool without loss of dye by 
pptn. in bath; sLuge (Cr) acid mordant dyes, fast to rubbing, crocking, light, and soap. 

S. 804—‘‘Alizarin Blue S.” Note 258,530 and 31 and 279,081, for soluble alizarin blue 
bisulfite comp., which is unstable at 100° and rubs off or crocks. 


555,904—Mar. 3, 1806. Heinrich LausmMann, Germany. 
Dye from dinitro-anthrachrysone-disulfo acid. (Process also claimed.) Probably 
diamino disulfo anthrachrysone. 

Dinitro ANTHRACHRYSON disulfo, derived from disulfo comp. by nitration, reduced in alk. 
Na,S soln. at ordinary temp., then on water bath. A black cryst. powd. sol. in hot aq. (VB), in 
dil. alk. (RV), in conc. sulf. (VR), diff. sol. glac. acetic (R), insol. in other usual organic sol- 
vents, completely absorbed by wool from acid bath, giving green tints with CrF,; a GREEN acid 
and acid mordant (Cr) dye, fast to milling and light. 


14 DIGEST OF PATENTS 


569,404—Oct. 13, 1806. Richard Brascu, Germany. (Hochst.) 
Alizarin dye and method of making same. 4-Amino alizarin mixture, or derivs. 


Benzoyl aLizaR1In derived from the commercial ALIZARIN by heating with BENzoyL chloride, 
or the flavopurpurin or anthrapurpurin derivs., added in powder form to nitration mixture 
below 5° and after standing heated to 20-30°, separated, saponified and reduced. Table of re- 
actions and numerous properties of three products are given. Dyes are insol. in aq., diff. sol. in 
alc., ether, and C,H,; and are rEp (Al) acid mordant dyes. ' 


569,405—Oct. 13, 1806. Richard Brascu, Germany. (Héchst.) 


Green alizarin dye and method of making same. Alizarin 4-quinolin, or 1.2-dioxy- 
anthraquinolin, isomers and derivs. 


4-Amino ALIZARIN, 4-amino flavopurpurin or 4-amino anthrapurpurin or their 4-nitro com- 
pounds, 1 part, heated at 110-120° in 7-10 parts 66° sulfuric acid soln. with 1 part each of 
GLYCERIN and nitrobenzene, or with 3 parts glycerin only when nitro comps. are treated. The 
bisulfite comps., easily sol. in aq., are obtained by prolonged treatment of the finely divided color 
with conc. solns. of alkali bisulfites at 0°-50°, filt. and pptd. by salt. Properties of various dyes 
are given. The free alizarin deriv. is insol. in aq., diff. sol. in organic solvents, sol. in conc. 
sulf. (R), in alk., bisulfites (R); a GREEN (Cr) acid mordant dye. 

Near S. 803—‘‘Alizarin Blue X.” Note 569,904. 


569,418—Oct. 13, 1896. Heinrich LAUBMANN, Germany. (Hochst.) 


Blue dye and method of making same. Diamino anthrachrysone disulfo, sodium salt. 


Dinitro ANTHRACHRYSONE disulfo made as in 569,419, reduced with acid and Fe or Zn, 
then heated with alk. carbonates. A red cryst. powd., sol. in hot aq. (R), in dil. alk. (B), in 
conc. sulf. (VR), very slightly sol. in alc. or acetone, insol. in usual organic solvents; an acid 
or acid mordant dye, ranging from BLUE to vIOLET when after treated with various mordants. 


595,349—Dec. 14, 1897. Robert E. Scumipt, Germany. (Bayer.) 
Dinitroanthrachrysone-disulfonie acid and method of making same. Dinitro 
anthrachrysone disulfo. 


ANTHRACHRYSONE sulfonated in 4-5 parts oleum (ten to twenty per cent SO,) at 100°, 
then nitrated by slowly adding the sulf. acid soln. after diln. with 66° acid, to the theoretical 
amount of HNO, for two nitro groups, and heating to 80° Product is easily sol. in aq. and alc., 
ether, benzene, CHCl, glac. acetic, in alk. (R), decomp. fee 230°, the Na salt cryst. in yellow 
leaflets. Reduction in acid soln. with Fe or Zn then boiling with alks. yields deep BLUE to 
VIOLET acid dyes. 

Note employment of above in dyestuff 569,418. 


595,349—Dec. 14, 1807. Robert E. ScumMipt, Germany. (Bayer.) 
Anthrarufin dye. (Process also claimed.) Disulfo acid of 4.8-dioxy 1.5-diamino anthra- 
quinone. 


ANTHRARUFIN disulfonated in 4 parts oleum (twenty per cent SO,) at 100-120°, diluted with 
66° acid, cooled, and at 20-30° mixed acid containing 2 mols. HNO, added and further heated 
to 60°. The Na salt is separated and reduced in aq. soln. with SnCl, and HCl. Product is a 
dark blue powd., easily sol. aq. (B) and pptd, by acids, sol. dil. NaOH (GB), in conc. sulf. (Y), 
changing with boric acid to (GB) with characteristic absorption spectrum; a BER) acid or green 
BLUE (Cr) acid mordant dye, fast to light and fulling. 

S. 858—“Alizarin Saphirol B.”’ Note 595,350. 


595,350—Dec. 14, 1897. Robert E. Scumipt, Germany. (Bayer.) 
Blue dye from chrysazin. (Process also claimed.) Disulfo acid of 1.8-dioxy 4.5 diamino 
anthraquinone. 


Curysazin sulfonated in 4 parts oleum (twenty per cent $O,) at 100-120°, diluted with 
6 parts 66° sulfuric and 2.5 parts mixed acid containing 2 mols. HNO, added at 20-30° then 
let stand until reaction is complete. The K salt is formed, separated as yellow crysts, and 
reduced in aq. soln. with SnCl, and HCl. A violet powd. of coppery luster, sol. in aq., pptd. by 
acids, sol. conc. HCl (Y), aera: on diln., sol. conc. sulf. (Y), not changed with boric acid, sol. 
in alk. (GB), insol. glac. acetic and C,H,; a BLuE acid dye or green Biux (Cr) acid mordant dye. 

Note 595,349. 


GROUP III.—ANTHRAQUINONE 15 


599,425—Feb. 22, 1808. Robert E. Scumipt, Germany. (Bayer.) 
Blue-black alizarin dye. (Process also claimed.) 2.4-Dianilino 1-oxy anthraquinone and 
derivs. 


PuRPURIN 1 part, condensed in 10 parts ANILIN or other primary aromatic amin by heating 
with a little cryst. boric acid at 150-160°, to form boric ether mixture, cooled to 50°, poured 
into dil. HCl and ppt. filt., dried and sulfonated in 66° sulfuric at 20-60°. Process of purifica- 
tion of intermediates is given. Above product is dark powd., sol. in aq. (VR), in dil. NaOH 
(VB), in dil. NH,OH (VR) turning to (BV) with excess, easily sol. hot alc. (VR), decomp. 
when heated with H,SO, to 60°; a blue Gray to blue Black (Cr) acid mordant dye, fast to light, 
fulling, acids. 

S. 862—‘“‘Alizarin Blue Black B.”? Note 595,349 and so and 599,426 and 7. 


599,426—Feb. 22, 1898. Robert EK. Scumipt, Germany. (Elberfeld.) 


Green dye derived from anthraquinone. (Process also claimed.) Mono sulfo acid of 
1.4-ditoluidino anthraquinone. 


QUINIZARIN condensed with 2 mols. 4-ToLUIDIN or other primary aromatic amin, then 
purified and sulfonated in sulfuric mono-hydrate at 70-80°. Dark powds., sol. in aq. (G), reduced 
with Zn and HCl (Y), the green color restored by air, separating quinizarin hydride when 
heated in small amount of H,SO,, sol. in organic solvents (BG), in conc. H,SO, (B), turning 
to (G) when diluted; a blue GREEN acid dye, fast to light, acids, and alks. 

S. 865—‘‘Alizarin Cyanin Green B,’’ and S$. 852 “‘Alizarin Irisol D,” also S. 854, 855, and 
856. Note 599,425, 599,427, and 595,349-50. 


599,427—Feb. 22, 1808. Robert E. Scumipt, Germany. (Elberfeld.) 


Green dye derived from quinizarin. (Process also claimed.) Disufo acid of 1.4- 
ditoluidino anthraquinone. 


QUINIZARIN condensed in sulfuric acid soln. containing an equal wt. of cryst. boric acid, 
with 2 mols. 4-ToLUIDIN or other primary aromatic amin, then sulfonated strongly in 1o parts 
fuming sulf. (five per cent SO,) at common temp. or heated to 50-70°. A green powd., 
sol. in ag. (G), with Zn and HCl (Y) changing with air to (G), giving quinizarin hydride when 
heated with small quantity of sulf., sol. in alc. (BG), in CHCl, and acetone (G), in conc. sulf. 
(BG), turning to (G) on diln.; a creEn acid dye fast to light, air, acid, and alk. 

S. 865—‘‘Alizarin Cyanin Green E,” and S. 852 “Alizarin Irisol D,” also S. 854, 855 and 
856. Addition to 599,426. r 


603,659—May 10, 1898. Robert E. Scumipt, Germany. (Elberfeld.) 


Dark-green alizarin derivative. (Process also claimed.) Sulfo acid of ditolyl 5.8- 
diamino purpurin. 

AlizaRIN pentacyanin (1.2.4.5.8-pentaoxy anthraquinone) condensed with 2 mols. 4- 
TOLUIDIN, or other aromatic amin to form ditolyl 5.8-diamino 1.2.4-trioxy ANTHRAQUINONE, and 
heated at 70-80° in 10 parts conc. one hundred per cent sulfuric. Dark powds., sol. in aq. (G), 
giving leuco dye with Zn and acetic acid when followed by heating with dil. H,SO,; bright 
GREEN (Cr) acid mordant dyes, fast to light. 

Near S. 854—‘“‘Alizarin Viridin DG.” 


605,568—June 14, 1898. Robert E. Scumipt, Germany. (Elberfeld.) 
Anthraquinone dye. (Process also claimed.) Mono sulfo acid of 4.8-diamino anthrarufin. 


4.8-Diamino ANTHRARUFIN, sulfonated to mono sulfo acid, by heating to 120-130° in 20 
parts oleum (thirty per cent SO,) containing an equal wt. of boric acid, diluted largely, boiled 
and filt. A blackish powd., insol. in alc., ether, C,H,, C,H;NO, and glac. acetic, sol. in 
C,H,;NH, and C,H,N (GB), in dil. alks. (B), in conc. sulf. (Y) turning to (B) with boric acid, 
and showing characteristic absorption; a BLUE acid dye, fast to light, or green BLUE (Cr) acid 
mordant dye, fast to light and milling. 


605,921—June 21, 1898. Robert E. Scumipt and Paul Tust, Germany. (Elberfeld.) 
Blue anthraquinone dye. (Process also claimed.) 4.§-Diamino chrysazin mono sulfo acid. 


4.5-Diamino CHRYSAZIN (1.8-dioxy 4.5-diamino anthraquinone), heated at 120-130° in 20 
parts oleum (thirty per cent SO,) containing 1 part boric acid. A blackish powd., sol. in 
C,H,NH,, C,H,N, and dil. alk. (B), in conc. sulf. (Y), which with boric acid becomes (VR); 
a BLUE acid dye, fast to light, or green BLUE (Cr) acid mordant dye, fast to light and milling. 


16 DIGEST OF PATENTS 


608,238—Aug. 2, 1808. Karl Tuun, Germany. (Elberfeld.) 
Green alizarin dye. (Process also claimed.) Sulfo acid of 5.8-ditoluidino alizarin. 


ALIZARIN BORDEAUX (1.2.5.8-tetraoxy ANTHRAQUINONE), condensed with 2 mols. 4-TOLUIDIN or 
other primary aromatic amin, then sulfonated at 70-80° in mono-hydrate acid. A dark green 
powd., sol. in aq. (G), with Zn and acid (Y) and separating leuco alizarin bordeaux on heating 
with a little H,SO,; a GREEN acid or GREEN (Cr) acid mordant dye, fast to light. 


609,327—Aug. 16, 1808. Rene Boun, Germany. (Badische.) 
Blue-black dye and process of making same. 


1.8-Dinitro NAPHTHALENE, with or without (1.5) deriv., heated in alk. soln. with bisulfite and 
Na,S or other reducing agent, then made acid, boiled to drive off SO, and dye salted out. 
Dark powds., sol. in aq., in dil. NH, (B), in cone. H,SO, (B-BG fluor); violet BLUE to BLACK 
acid dyes. Properties of Schulz dye not same as those in patent. 

S. 742—“Printing Blue for Wool,” 743, ‘“Kryogen Brown A,’ or S. 776 “‘Printing Black for 
Wool.” Note 632,170 for treatment with Na,S and S, and 674,137 for similar patent (Gr. XV). 


617,686—Jan. 10, 1890. Max H. Iszter, Germany. (Badische.) 
Blue dye and process of making same. Diamino dioxy anthraquinone sulfo acids. 


1.5-Dinitro ANTHRAQUINONE, or other dinitro anthraquinones, heated with 10-20 parts 
fuming sulf. acid (thirty to forty per cent SO,), equal wt. boric acid and small amount of 
sulfur to 120-130°. Sulfur alone would give (VB) and boric acid alone (BrV) colors, while 
above yields (GB). Higher temp. and stronger acids yield redder shades. Products are sol. in 
conc. sulf. (Y), in NH,OH, NaOH or C,H,NH, (B), in alc. (BV), and in HCl (BrY); green 
BLUE to violet BLUE (Cr) acid mordant dyes, fast to fulling. 

S. 800 and 801—‘‘Anthracene Blue WG.” 


617,981—Jan. 17, 1899. Oscar Batty, Germany. (Badische.) 


Anthraquinone derivative and process of making same. Condensation of 1.5- 
dinitroanthraquinone sulfo acid with gallic acid or other phenolic deriv. 


1.5-Dinitro ANTHRAQUINONE, crude or its reduction product, heated below 130° with a little 
sulfur and 5 parts fuming sulf. (twelve to forty per cent SO,), with or without boric acid, cooled, 
and about 1 part GALLIc acid, or other phenol, sulfo or carboxy phenol or deriv. (see table of 
reactions) added, and mixture heated to 50-60°. <A black powd., sol. in aq. (V-B), with NaOH 
or Na,CO, (G-B); vIOLET to BLUE acid dyes or green BLUE, BLUE, or blue GREEN (Cr) acid 
mordant dyes. 


618,000—Jan. 17, 1880. Oscar Batty, Germany. (Badische.) 
Yellow dye and process of making same. 4.4’-Dihydroxy diphenyl 2.2'.6.6’-dilactone. 


3.5-Dihydroxy BENZOIC ACID or other aromatic hydroxy acid in 20 parts ninety-five per cent 
cold H,SO, oxidized by 1.5 parts persulfate below 50°, or by electricity in 4 parts sixty-three 
per cent sulf. at 10-20°, using a diaphragm and current of 8 volts and 20 amperes per sq. dem. 
anode surface or other suitable conditions. Yellow to green yellow paste or powd., diff. sol. 
in aq., sol. in conc. sulf. (Y), in Na,CO, (Y-G), pptd. by excess of latter (Br); vELLow (Cr) 
acid mordant dyes fast to light and milling . 

S. 771—“‘Resoflavin W.”? Note that Schulz gives the formula for a dye derived from 3.4- 
dihydroxy benzoic acid, not the sym meta form. 


619,114—Feb. 7, 1800. Oscar Batty, Germany. (Badische.) 


Green-black dye and process of making same. Probably 1.2.5.8-tetroxy 7-phenoxy 

naphthalene, or the 5.8-quinone deriv., etc. 

1.5-Dinitro NAPHTHALENE heated with fuming sulfuric acid and reducing agent to form 
NAPHTHAZARIN intermediate, then condensed in same soln. with PHENOL, homologs, analogs, or 
derivs. Dark brown paste or powds., sol. in hot aq., NaOH and Na,CO,, in cold C,H,NH, 
(V-B), in cone. sulf. (V-R-BrR), give sol. bisulfite comps., and leuco comps.; green BLACK (Cr) 
acid mordant dyes. 

S. 775—‘“‘Alizarin Dark Green W.’’ Note 619,115 for specific claims. 


619,115—Feb. 7, 1880. Oscar Batty, Germany. (Badische.) 


Bluish dye and process of making same. (Process not claimed.) 1.2.5.8-Tetroxy 7- 
naphthoxy naphthalene. ; 


1.5-Dinitro NAPHTHALENE heated with fuming sulfuric acid and reducing agent to form 


GROUP III.—ANTHRAQUINONE 17 


NAPHTHAZARIN intermediate which is condensed with 1-NAPHTHOL. A gray powd., easily sol. aq. 
(GB), in sulf. (RBr), little sol. in alc., in hot C,H,NH, (BG); a gray BLUE (Cr) acid mordant 
dye. 

S. 775—“‘Alizarin Dark Green W.” Note 619,114 for generic claims. 


619,574—Feb. 14, 1880. Max H. Ister, Germany. (Badische.) 
Xanthopurpurin sulfo-acid. 

1.3-Diamino ANTHRAQUINONE, mixed at common temp. with 10 parts fuming (twenty to forty 
per cent SO,) sulfuric acid and 1 part nitrite, then heated to 100—130° to form XANTHOPURPURIN 
sulfo acid, an important intermediate and also dye, which is sol. in aq. (GY), in NaOH (OR), 
insol. in alc., sol. in conc. sulf. (Y), turning to (Br) with boric acid; a dull yELLow acid dye. 


621,679—Mar. 21, 18909. Max H. Ister, Germany. (Badische.) 


Oxyanthraquinone sulfo acid and process of making same. Sulfo acid of an- 
thrarufin, also an important intermediate. 
1.5-(or 1.3 or 1.8) Diamino ANTHRAQUINONE or mono amino derivs. dissolved in 10 parts 
fuming sulfuric acid, (twenty to forty per cent SO,) at common temp., 1 part NaNO, added, 
and heated to 100-130° for 2.5 hours. Product is sol. in aq. (OY), in NaOH (VR), insol. in 
alc., sol. in sulf. (OY), which with boric acid becomes (VR with OY fluor); yELLow acid dyes. 


623,069—April 11, 1809. Rene Bown, Germany. (Badische.) 
Yellow dye and process of making same. Probably an oxy ketone or lactone dye. 

_ BENZALDEHYDE condensed with cyanide to BENZOIN, which in 66° sulfuric acid is condensed 
below 5° with Gatiic acid, dioxy benzoic acid or other aromatic oxy carbonic acid. Yellow 
paste, diff. sol. Na,CO, (YBr), in NaOH (R), in cone sulf. (Y-R with fluor); yELLow (Cr) 
acid mordant dye, fast to fulling. 

Near S. 762, 770 or 771. Note 618,000 


623,219—Apr. 18, 1809. Robert E. Scumipt, Germany. (Elberfeld.) 
Chrysazin dye and process of making same. Ammonium salt of disulfo acid of 4.5- 

dioxy amino chrysazin. 

4.5-Dinitro CHRYSAZIN disulfo acid in 50 parts aq., reduced by SnCl, and HCl to hydroxyl- 
amin form by using such quantity of reducing agent as corresponds to 8 atoms of H only. 
After heating to 50-60°, conc. NH,Cl is added to form ammonium salt. A dark powd., sol. 
in aq. (V), changing to (G) with NaOH, sol. in conc. sulf. (Y), when reduced becomes diamino 
comp.; a BLUE acid or blue GREEN (Cr) acid mordant dye. 

Note 595,350 and 623,220. 


623,220—April 18 1899. Robert E. Scumipt, Germany. (Elberfeld.) 
Anthrarufin dye and process of making same. Disulfo acid of 4.8-dioxy amino 
anthrarufin. 


4.8-Dinitro ANTHRARUFIN disulfo acid is carefully reduced by SnCl, and HCl to dihydroxyl- 
amin compound, using sufficient reducing agent to supply 8 atoms of H only, mixture heated 
to 50-60° and NH,CI or other alk. chloride added to form salt. A dark powd., sol. in aq. (B), 
changing to (BG) with NH,, sol. in conc. sulf. (Y), can be reduced to diamino deriv.; a violet 
BLUE acid or blue GREEN (Cr) acid mordant dye. 

Addition to 623,219. 
623,638—Apr. 25, 1899. Karl Tuun, Germany. (Elberfeld.) 
Gray-black anthraquinone dye and process of making same. Mono or dinitro 

sulfo deriv. of 1-oxy 2.4-dianilino anthraquinone. 

PURPURIN and 2 mols. ANILIN condensed in sulfuric acid to dianilid, then heated in 20 parts 
66° H,S0, to 60° until readily water sol., 1 part boric acid added, cooled to 10° and mixed 
acid containing 1-2 mols. HNO, stirred in for 1 hour, diluted, and pptd. by salt. Dark powds., 
sol. conc. sulf. (R-B), which soln..decomp. on heating to regenerate purpurin; GRAY to BLACK 
(Cr) acid mordant dyes, fast to fulling, acids and light. 

Note 599,425. 
627,896—June 27, 1899. Rene Bown, Germany. (Badische.) 
Blue dye. Sulfonated naphthazarin or its leuco form. 

1.5 and 1.8-Dinitro NAPHTHALENE, heated in sulfuric soln. with Zn or sulfur, etc., to form 
NAPHTHAZARIN intermediate leuco comp., which is heated at 100° in 10 parts fuming sulfuric 


18 DIGEST OF PATENTS 


acid, (twenty-three per cent SO,). The dye which may be applicd direct to fiber or as leuco 
deriv., forms cryst. nedles, is sol. in aq. (B), in conc. sulf. (Y), in hot dil. H,SO, (VR), in dil. 
NaOH (B), pptd. by excess; a BLUE acid or acid mordant dye. 


631,605—Aug. 22, 1890. Oscar Batty, Germany. (Badische.) 
Green dye and process of making same. Anilino derivs. of alphylated diamino anthra- 
quinones. 


1.5-Dinitro ANTHRAQUINONE condensed with ANILIN or other primary aromatic amin, then 
brominated or chlorinated and condensed with ANILIN or other amin by boiling for 4 hours in 
10 parts of the amin. Product may be sulfonated by usual methods. In unsulfonated form 
these dyes are insol. in aq. and alc., more sol. in C,H,, C,H,NO, and C,H,NH,, and in sulfonated 
form are sol. in hot aq. not changed by alk.; GREEN acid or acid mordant (Cr) dyes, fast to light. 
For halogenated alphyl amino anthraquinone see 631,606. 


631,613—<Aug. 22, 1800. Rene Boun, Germany. (Badische.) 
Black dye and process of making same. Anilin deriv. of naphthazarin. 


NAPHTHAZARIN, twenty per cent paste, condensed in glac. acetic soln. by heating to 40° with 
equal weight ANILIN, using equal wt. boric acid as condensing agent. Other condensing agents 
and other amins are claimed and dyes may be sulfonated. (See table of reactions). A brown 
paste or powd., sol. in aq., in cold conc. sulf. (Br), which on heating is (V), in NaOH (RV-BG); 
a BLUE (Cr) acid mordant dye in unsulfonated form and sLack (Cr) acid mordant when sul- 
fonated. 


631,614—Aug. 22, 1800. Rene Boun, Germany. (Badische.) 


Naphthazarin intermediate dye and process of making same. Leuco form of 

‘“‘naphthazarin intermediate’? used as dye, and bisulfite compound thereof. 

1.5-Dinitro NAPHTHALENE heated in fuming sulfuric with reducing agent to form “‘NAPH- 
THAZARIN intermediate,” diluted, filt. and converted to leuco comp. by reduction with SnCl,, or 
other reducing agent. Product is bluish white, sol. in Na,CO, (RV), in NaOH (R) becoming 
(BV) in air and pptg., diff. sol. in aq., sol. conc. sulf. (R), turning (Br) when heated; a green 
BLUE (Cr) acid mordant dye. : 

S. 774—“‘Alizarin Black WR.” 


632,621—Sept. 5, 1899. Oscar Batty, Germany. (Badische.) 
Brominated dye. ‘Trianilin 1.5-diamino anthraquinone. 


Tribrom deriv. of 1.5-diamino ANTHRAQUINONE, heated to boil in 10 parts ANILIN or other 
aromatic amin until uniformly blue, cooled, filt., and product sulfonated in 20 parts ninety-six 
per cent H,SO, at common temp. Other’ amins and sulfo derivs. are claimed. In unsulfonated 
form products are sol. in C,H,NH, (GB), in C,H;NO, (BG), in hot conc. sulf. (RV), in the 
sulfonated form sol. in aq. (B), not changed by NaOH, sol. conc. sulf. (R), gives leuco comps.; 
BLUE to green BLUE acid or acid mordant (Cr) dyes. 

S. 861—‘‘Anthraqttiinone Blue SR.” For mfr. of tribrom anthraquinone anilin deriv., see 
631,608. Schulz gives tetra brom deriv. 


633,950—Sept. 26, 1899. Rene Boun, Germany. (Badische.) 
Green-blue dye and process of making same. Oxidized “naphthazarin intermediate.” 
NAPHTHAZARIN intermediate melt, from 1.5-dinitro NAPHTHALENE by heating in sulfuric 


acid with reducing agent, is diluted strongly and oxidized by hypochiorite, bichromate, or other 
oxidizing agent. Bisulfite comp. may be formed. Properties of the naphthazarin intermediate 
are given (see also 631,614). Dye forms a green blue paste, sol. in Na,CO, (BV), in NaOH (B), 
little sol. in cold aq., on boiling (B), in conc. sulf. (Br); green Brug (Cr) acid mordant dye. 


640,986—Jan. 9, 1900. Oscar Batty, Germany. (Badische.) 
Green dye. Tetra toluidino 1.5-diamino anthraquinone and sulfo derivs., homologs and 
analogs. 


1.5-Diamino ANTHRAQUINONE in glac. acetic soln. through which chlorine is passed to form 
tetra chlor deriv., which is condensed by heating to boil with 4-roLuipIN or other aromatic amin 
and may be sulfonated. In unsulfonated form dye is insol. in cold aq., sol. cold conc. sulf. 
(BrG), which at 100° is (V) and with boric acid is (G), in sulfonated state is sol. in ag. (GB). 
unchanged by NaOH, with conc. H,SO, is (V); a GREEN acid dye. 


GROUP III.—ANTHRAQUINONE IQ 


643,451—Feb. 13, 1900. Oscar Batty, Germany. (Badische.) 


Nitroamidoanthraquinone sulfo-acid. Nitro deriv. of sulfonated 1.5, 1.3 or 1.8-dia- 
mino anthraquinones. 


1.5, 1.3-0r 1.8-Diamino ANTHRAQUINONE, mixed with equal wt. boric acid and added to 
mixture of 20 parts sulfuric monohydrate and 20 parts fuming sulfuric (forty per cent SO,), 
heated to 115° till soluble, cooled, 1 mol. HNO, as mixed acid added below 10°, diluted, and 
dye salted out. Products are sol. in aq. (RV), in Na,CO, and NaOH (BV), in conc. sulf. (V); 
blue VIOLET, brown VIOLET to violet BRowN acid mordant (Cr) dyes, fast to light. 


644,333—Feb. 27, 1900. Conrad Scurause, Germany. (Badische.) 
Yellow dye. 8-Oxy 1.2-phenanthro naphthazin sulfo acids. 


SuLFANILIC acid azo 2-AMINO 8-NAPHTHOL, reduced in acetic soln. with Zn dust to form 
1.2-diamino 8-naphthol, filt., filtrate added to 1 mol. PHENANTHRENE quinone in 50 parts of ten 
per cent bisulfite soln. warmed to 90-95° and pptd. product added to 5 parts oleum ( twenty- 
five per cent SO,), at 40°. Other components claimed, and sulfonation may take place before 
condensation. Products are sol. in aq. (Y), pptd. by NaOH (Y) but sol. on heating (OY), 
sol. in 40° HNO, (R), in conc. sulf. (BV); fast yELLow acid dyes. 


646,795—Apr. 3, 1900. Rene Boun, Germany. (Badische.) 


Naphthazarin sulfo-acid and process of making same. Sulfo acid of naphthazarin 

differing from that of 627,896. 

NAPHTHAZARIN sulfo, the blue dye of 627,896, is boiled in 50 parts very dil. HCl till blue 
color becomes red, and pptd. by KCl. The new sulfo dye that results is a brown red powd., sol. 
in aq. (VR), in dil. NaOH (B), in conc. sulf. (VR); a brown rep acid or deep Brack (Cr) 
acid mordant dye, fast. 

Note 631,614 and 646,706. 


646,796—Apr. 3, 1900. Rene Boun, Germany. (Badische.) 


Green dye and process of making same. Sulfo acid of sulfonated “naphthazarin inter- 
mediate,’’ condensed with anilin or other aromatic amin. 

NAPHTHAZARIN sulfo, the blue dye of 627,806, boiled 1 hour with 10 parts ANILIN and 4 
parts ANILIN HCl, diluted, pptd. by HCl, filt., dried, and sulfonated in 20 parts ninety-six per 
cent H,SO, by heating for 24 hours to 30-40°. Other aromatic amins may be used. Black 
powds., sol. in aq. (G), in glac. acetic (BG), in conc. sulf. (BrR), in dil. NaOH (G); GREEN 
acid dyes. 

Note 631,614 and 646,795. 


647,370—Apr. 10, 1900. Rene Boun, Germany. (Badische.) 


Green dye. Sulfo acid of “naphthazarin intermediate’ condensed with anilin or other aro- 
matic amin. 

NAPHTHAZARIN intermediate, produced as in 631,614, dissolved in 20 parts boiling glac. acetic 
acid, 2 parts ANILIN or other aromatic amin added and heated at r1oo° till color change to green 
is complete. Product is sulfonated by heating in ninety-five per cent sulfuric at 40-50° for 
12 hours. In the wunsulfonated form product is insol. in aq. and dil. NaOH, sol. in conc. 
sulf. (GB), in C,H,;NH, (G), no claims made as dye; in sulfonated form sol. in aq. (BG), 
turning with Na CO, or NaOH to (G), in conc. sulf. (B); GREEN acid dyes. 

Note CE me 795 and 6. 


648,271—Apr. 24, 1900. Heinrich LaupMann, Germany. (Hochst.) 
Oxyanthraquinone disulfonic acid and process of making same. _1.2.4.5.6-Pen- 
taoxy 3-7-disulfo anthraquinone, or iso comp. 

ANTHRAFLAVIC acid, tetraoxy ANTHRAQUINONE disulfo, or isoOANTHRAFLAVIC acid oxidized to 
pentaoxy compound in 10-20 parts 66° sulfuric acid soln. with 1 mol. MnO, or HNO,, etc. The 
acid alkali salt is a red cryst. powd., sol. in hot aq. (R), turning (Br) with NH, or dil. Na,CO,, 
or (RV) with caustic, pptd. by excess (R), sol. in conc. sulf. (VR); a RED acid ee or BLUE (Cr) 


acid mordant dye, fast to milling. 
Note 656,463. 

648,331—Apr. 24, 1900. Oscar Bauuy, Germany. (Badische.) 

Blue anthraquinone dye. Halogen deriv. of dialphylamino anthraquinone, oxidized and 
sulfonated. 


1.5-Dianilino ANTHRAQUINONE, Br deriv. or other halogen or alphylamino derivs., oxidized 


20 DIGEST OF PATENTS 


in 20 parts ninety-six per cent sulf. acid containing 1 part boric acid, then sulfonated by adding 
z0 more parts fuming sulf. (forty per cent SO,) and heating to 130° till readily sol. in aq. See 
table of reactions of various products, which are dark pastes or powds., sol. in ag. (B), in dil. 
NaOH (B-G), in conc. sulf. (G), in ale. (B-V), in C,H,NH, (B); violet BLUE to blue GREEN 
acid or acid mordant (Cr) dyes. 

Note 631,606 and for specific claims 648,332. 


648,332—Apr. 24, 1900. Oscar Batty, Germany. (Badische.) 

Violet anthraquinone dye. Halogen 1.5-diamino anthraquinone, oxidized and sulfonated. 
1.5-Diamino ANTHRAQUINONE bromide, or other halogen deriv. obtained by halogenation in 

glac. acetic soln., mixed with equal parts boric acid added to 20 parts ninety-six per cent H,SO,, 

and heated to 100° till blue. Twenty parts fuming H,SO, (forty per cent SO,) are further 

added and temp. raised to 130°. Product is sol. in hot aq. (VB), in dil. NaOH (B), in alc., 

(BV), in anilin (B), in conc. sulf. (Y); vioretT acid dye or violet BLUE (Cr) acid mordant dye. 
Note 631,607 and 631,608, also 648,331, which gives general claims. 


650,756—May 29, 1900. Max H. Ister, Germany. (Badische.) 
Mordant-dyeing red color and process of making same. Insoluble hexa oxy an- 
thraquinone differing from those previously produced. 

Dinitro ANTHRAQUINONE, oxidized by heating at 140-150° in fuming sulfuric acid (forty- 
five per cent SO,), containing boric acid and sulfur as in 617,686, then more acid (sixty-three per 
cent SO,) added and heated to 130-140°. Product is insol. in aq. and HCl, sol. in conc. sulf. 
(RV), cryst. from C,H,NO, gives green crysts. containing neither nitrogen nor sulfur; a RED 
(Al) acid mordant dye. 


653,492—July 10, 1900. Paul UnuMann, Germany. (von Heyden.) 


Betanaphthoquinone dye and process of making same. b-Naphthoquinone oxi- 
dized and probably condensed. 
b-NAPHTHOQUINONE, and derivs., oxidized by heating in fuming sulf. acid (five per cent 
SO,) containing boric acid, the proportions of boric and the degree of conc. of the acid and the 
period of operation may vary within wide limits and influence the shade. Red black to violet 
pastes slightly sol. in aq., sol. in NaHCO, (BBk), in Na,CO, (GB), in NaOH (G), in cone. sulf. 
(Bk); BLUE, green BLACK to BROWN acid mordant (Al, Fe, Sn) dyes. 


654,294—July 24, 1900. Oskar Uncrr, Germany. (Elberfeld.) 
Blue anthraquinone dye and method of making same. Ditoluidino 1-amino an- 

thraquinone sulfo or other aryl amino deriv. 

1-Amino ANTHRAQUINONE dibromide, a dark red powd. or brick red needles, m. p. 221°, re- 
fluxed with 4-ToLUIDIN, or any aromatic amin till sol. in CHCl, with blue color, then pptd. by 
alcohol and sulfonated in fuming acid (twenty per cent SO,) at 50-70° till sol. in aq. Dark 
powds., diff. sol. alc. and ag. (B), in HCl (OR), sol. in NH,OH (B), in conc. sulf. (B), pptd. 
on diln. (B); a BLUE acid or acid mordant (Cr) dye. 


654,295—July 24, 1900. Oskar Uncer, Germany. (Elberfeld.) 


Green anthraquinone dye and method of making same. Probably disulfo derivs. 
of 1.4-ditoluidino anthraquinones. 


1-Nitro ANTHRAQUINONE and 4-TOLUIDIN condensed to form an aryl 1-amino anthraquinone, 
brominated, boiled with 4-toluidin or other aromatic amin and sulfonated. Dark powds., sol. in 
aq. and NH, (BG), in alc. (G), in conc. sulf. (G), pptd. on diln. (G); GreEN acid or acid 
mordant (Cr) dyes. 

Near S. 865—‘“‘Alizarin Cyanin.”” Note 599,426 and 27, and 654,294. 


654,505—July 24, 1900. Oscar Batuy, Germany. (Badische.) 


Mordant-dyeing coloring matter. Schulz 801 gives formula as diamino dioxy anthra- 
quinone sulfo acids which are treated with NH, under pressure. 


“ANTHRACENE BLUE G,” from dinitro ANTHRAQUINONE treated with sulf. acid containing 
boric acid and sulfur, or similar coloring matter, with 10 parts twenty per cent ammonia and 
2 parts NaOH heated at 150° in an autoclave at from 5-20 atmos. Dark bronzy powds., only 
slightly sol. hot aq., sol. in Na,CO, and NaOH (B), in sod. acetate (VB), in alc. (V), in 
anilin (B), in conc. sulf. (OR); green sLuE (Cr) acid mordant dye. 

S. 802—‘‘Anthracene Blue WG.” Addition to 617,686. 


GROUP III.—ANTHRAQUINONE 2I 


654,506—July 24, 1900. Oscar Batty, Germany. (Badische.) 
Dye from anthracene-blue. (Process also claimed.) Diamino dioxy anthraquinone sulfo 
further oxidized and heated under pressure with NaOH. 

ANTHRACENE BLUE G (S. 801), derived from dinitro ANTHRAQUINONE heated in sulfuric acid 
soln. with boric acid and sulfur, or homolog, heated in autoclave at 165° with twenty per cent 
NaOH soln., or boiled in strong NaOH soln. Dark powds. of metallic luster, almost insol. boil- 
ing aq., sol. in sod. acetate (RV-V), in Na,CO, (VB), in NaOH (B), in conc. HSOe CR-V); 
BLUE (Cr) acid mordant dyes, fast to milling. 

S. 807—‘“‘Anthracene Blue WG.” Addition to 654,505. 


656,081—Aug. 14, 1900. Oscar Batty, Germany. (Badische.) 
Sulfonated anthraquinone dye, Alphylamino anthraquinone 1- or 2-sulfo acids. 

Nitro ANTHRAQUINONE sulfo (beta and alfa) heated in 10 parts 4-TOLUIDIN, or any aromatic 
amin, until color is uniform. Brown violet cryst. powd., sol. in aq. (V), in dil. Na,CO, (RV), 
in NaOH (V), pptd. by excess, sol. in alc. (VR), in conc. sulf. (Br); RED, VIOLET or BROWN 
acid or acid mordant (Cr) dyes. 

Addition to 654,505. 


656,463—Aug. 21, 1900. Heinrich LauBMann, Germany. (Hochst.) 
Tetraoxyanthraquinone disulfonic acid and process of making same. Tetra 
oxy disulfo anthraquinone. 

ANTHRAFLAVIN OF iSO ANTHRAFLAVIN acids, sulfonated in 8-10 parts fuming acid (ten to 
twenty per cent) at 110-120°, dinitrated by adding mixed acid, reduced with SnCl, and oxidized 
under various conditions to the tetra oxy deriv. Products are sol. in hot aq. (OY) as acid 
salt and (R) as normal salt, sol. in conc. sulf. (OR); yellow BRowN to orange BROWN acid dyes 
or vioLeEtT (Cr) or RED (Al) acid mordant dyes. 


656,668—Aug. 28, 1900. Robert E. Scumipt, Germany. (Elberfeld.) 
Blue anthrarufin dye and process of making same. Benzylated 4.8-diamino an- 

thrarufin disulfo. 

4.8-Diamino ANTHRARUFIN disulfo condensed with BENzyt chlorid in 50 parts aq. at 80-90° 
till reaction is complete by test. A blue powd., sol. in aq. (B), pptd. by conc. HCl (B), easily 
sol. alc., in conc. sulf. (Y), changed with boric acid to (G); a BLUE acid or green BLUE (Cr) 
acid mordant dye. 

Note 595,349 and 656,669. 


656,669—Aug. 28, 1900. Robert E. Scumipt, Germany. (Elberfeld.) 
Blue chrysazin dye and process of making same. Benzylated 4.5-diamino chrysazin 
disulfo acid. 


4.5-Diamino cHRYSAZIN disulfo condensed with pENzyL chlorid in 50 parts aq. at 80-90°. A 
blue powd. sol. in aq. (B), pptd. by HCl (B), sol. dil. NaOH (B), in conc. sulf. (Y) changing 
with boric acid to (OY); a BLUE acid or green BLUE (Cr) acid mordant dye. 

Note 595,350 and 656,668. 


656,670—Aug. 28, 1900. Robert E. Scumipt and Paul Tust, Germany. (Elberfeld.) 
Blue anthrarufin dye and process of making same. Brom diamino anthrarufin sulfo. 
Brom dinitro ANTHRARUFIN sulfo reduced in 100 parts aq. at 50-60° to diamino product by 
SnCl, and HCl. A dark blue powd., diff. sol. aq. (B), sol. in dil. alk. (B-GB), in conc. sulf. 
(Y) Piecing with boric acid (R-B); a BLvE acid or fast green BLUE (Cr) acid mordant dye. 
Note 656,730. 
656,730—Aug. 28, 1900. Robert E. Scumipt and Paul Tust, Germany. (Elberfeld.) 
Blue chrysazin dye and process of making same. Brom diamino chrysazin sulfo. 
Brom dinitro curysazin sulfo reduced with SnCl, and HCl in 100 parts aq. at 50-60° to di- 
amino product. A dark blue powd., easily sol. hot aq. (B), in dil alk. (B), in cone, sulf.. (CY) 
changing with boric acid (Rt); a BLUE acid or fast green BLUE (Cr) acid mordant dye. 
Addition to 656,670. 
658,513—Sept. 25, 1900. Robert E. Scumipt, Germany. (Elberfeld.) 
Blue chrysazin dye and process of making same. Bisulfite compound of 4.5- 
diamino chrysazin disulfo, condensed with formaldehyde. 
4.5-Diamino cHRYSAzIN disulfo, heated with FORMALDEHYDE in forty per cent bisulfite eal 


22 DIGEST OF PATENTS 


A dark blue powd., easily sol. in aq. (GB), not changed by HCl, when heated with fifteen per 
cent HCl split up with regeneration of the diamino chrysazin disulfo acid; a green BLuE acid dye. 
For chrysazin deriv. note 595,350, and also note 658,514. 


656,514—Sept. 25, 1900. Robert E. Scumipt, Germany. (Elberfeld.) 
Anthrarufin dye and process of making same. Bisulfite compound of 4.8-diamino an- 
thrarufin disulfo condensed with formaldehyde. 

4.8-Diamino ANTHRARUFIN disulfo heated in forty per cent bisulfite soln. with FORMALDEHYDE. 
A dark blue powd., easily sol. in aq. (GB), not changed by HCl, decomp. on heating with 
fifteen per cent HCl to form original diamino anthrarufin disulfo acid; a green BLUE acid dye. 

Addition to 658,513. 
659,565—Oct. 9, 1900. Oscar Batuy, Germany. (Badische.) 
Violet-red dye ard process of making same. (Process not claimed.) Mono sulfon- 
ated 1.5-dianilino anthraquinone and other dialphylamino derivs. 

1.5-Dinitro ANTHRAQUINONE condensed with ANILIN or other aromatic amin, then sulfonated 
moderately in 10 parts ninety-six per cent H,SO, at 90-100°, until sol. in aq. Products are sol. 
in hot aq. (R), not changed by Na,CO, or NaOH, sol. in alc. and warm anilin (R), in conc. 
sulf. (Br); violet rED acid dyes. 

S. 853—‘‘Anthraquinone Violet.”’ Note 631,605, 631,606 and 650,566. 


659,566—Oct. 9, 1900. Oscar Batiy, Germany. (Badisehc.) 
Yellow-red dye and process of making same. (Process not claimed.).) Disulfonated 
1.5-dianilino anthraquinone. 
1.5-Dinitro ANTHRAQUINONE condensed with aniILIN or other, then sulfonated strongly in 
fuming sulf. (twenty per cent SO,) at 30-35° till sol. Dark powds., easily sol. in aq. (OR) 
changing with NaOH to (VRt), insol. in alc., and anilin, sol. in conc. sulf. (R); orange rep 


acid dyes. 
S. 853—‘‘Anthraquinone Violet.’ Addition to 650,565. 


666,594—Jan. 22, 1901. Oscar Batty, Germany. (Badische.) 
Violet anthracene dye. Alphylamino derivs. of 1- or 2-amino anthraquinone sulfo acids. 

Brom 1-amino ANTHRAQUINONE sulfo, or similar comp., condensed with 4-ToLUIDIN, or other 
aromatic amin, by boiling in 10 parts of the amin, excess of which is removed by soln. in ether, 
benzene, alc., etc. Products are sol. in aq. (B-VB), sol. in dil. Na,CO, or NaOH but not in 
excess, sol. in alc., (BV), in conc. sulf. (Br); vioLET to BLUE acid or acid mordant (Cr) dyes. 


666,702—Jan. 29, 1901. Robert E. Scumipt and Andreas Jacosi, Germany. (Elberfeld.) 
Anthraquinone dye and process of making same. _ 1-oxy 2-sulfo 4-toluidino an- 

thraquinone and other alphylamino derivs. 

4-Nitro 1-oxy ANTHRAQUINONE 2-sulfo formed by sulfonating then nitrating erythoxy 
ANTHRAQUINONE, condensed with 4-ToLUIDIN or other primary aromatic amin, by heating at 
100° for 2-3 days in 20 parts fifty per cent acetic acid and 1o parts of the amin, and pptd. by 
dil. HCl. Dark blue powds., sol. in aq. (B) in dil. NaOH (BG), in conc. sulf. (G) changing 
with boric acid (B); violet BLUE acid and green sLUuE (Cr) acid mordant dyes. 


668,445—Feb. 19, 1901. Arnold Hxss, Germany. (Hochst.) 
Blue wool-dye and process of making same. Sulfo acids of tri-alphyl amino 
napthazarins. 


NAPHTHAZARIN intermediate boiled with 5 parts ANILIN (3 mols.) and 1 part ANILIN salt till 
violet blue, pptd. by HCl and product mixed with 10 parts sulfuric monohydrate at common 
temp. till sol. in aq. Other primary aromatic amins may be used. Blue black powds. of metallic 
luster, easily sol. aq. (B) not changed by alk.; sLug acid and fast Gray (Cr) acid mordant dyes. 

Note 669,894. 
669,894—Mar. 12, 1901. Rene Boun, Germany. (Badische.) 
Blue dye of naphthalene series and process of making same. Alphyl amino 
derivs. of naphthazarin sulfo acids. 


NAPHTHAZARIN sulfo produced as in 631,614 and 627,896, boiled in 50 parts aq. with 2 parts 
ANILIN HCl, or hydrochloride of other aromatic amin. A brown powd. of metallic luster, sol. in 
hot aq. (VB), turning with NaOH to (B), sol. in conc. H,SO, (V), in NaOH and anilin (B); 


BLUE acid dyes, fast to light. 


GROUP III.—ANTHRAQUINONE 23 


673,691—May 7, 1001. Oscar Batty, Germany. (Badische.) 


Anthraquinone dye. Alphyl amino derivs. of diamino anthraquinones, isomeric with pre- 
ceding patents. 


1.8, 1.3 or 1.5-Diamino ANTHRAQUINONE halogenated as in 631,607, 631,608, and 640,986, is 
condensed with 4-ToLuIDIN, or other aromatic amin by boiling in 10 parts of the amin until 
blue green, then pptd. by alc. Products may be sulfonated. The unsulfonated dyes are sol. in 
C,H,NH, and C,H,NO, (B-G) in cold conc. sulf. (Br-G), on heating to 100° (V-B), on addition 
of boric acid (B-G), in sulfonated form sol. in aq.; BLUE to GREEN acid or acid mordant (Cr) 
dyes. 

Note 632,621. 


675,572—June 4, 1901. Robert E. Scumipt, Germany. (Elberfeld.) 
Anthraquinone dye and process of making same. Sulfonated 1-amino 4-toluidino 
anthraquinone. 


1-Amino 4-Oxy ANTHRAQUINONE or I-nitro 4-amino anthraquinone, condensed with 4-ToLUIDIN 
or other aromatic amin by heating to 140-160° with 10 parts of the amin and o.5 part boric 
acid, pptd. by alc. and sulfonated by heating to 60-100° with 10-20 parts sulfuric monohydrate. 
Dark powds., sol. in hot aq., in NH,, in ninety per cent alc., in fifty per cent acetic (B), turn- 
ing redder with HCl, sol. in conc. sulf. (V) changing to red and pptg. on diln.; BLuE acid or 
acid mordant (Cr) dyes, fast-to light and alks. 


675,573—June 4, 1901. Robert E. Scumipt and Andreas JaKopi, Germany. (Elberfeld.) 


Anthraquinone dye and process of making same. _ 1.4.5.8-Tetra toluidino anthra- 
quinone, its sulfo acids and isomers. 


1.5-Dichlor 4.8-dinitro ANTHRAQUINONE or other alfa dihalogen dinitro derivs., condensed 
with 4-TOLUIDIN, or other primary aromatic amin by heating to 140-180° with 10 parts of the 
amin, pptd. by HCl and product heated at 80-100° in 10 parts sulfuric monohydrate. Dark 
powds., sol. in aq. and NH,(YG-GB), diff. sol. in alc. (GB), sol. in conc. sulf. (GB), pptd. on 
diln. (G); yellow GREEN to blue GREEN acid or acid mordant (Cr) dyes. 

Note 675,572-74-75. 


675,574—June 4, 1901. Robert E. Scumipt and Paul Tust, Germany. (Elberfeld.) 
Anthraquinone dye and process of making same. Ditoluidino anthraquinone sulfo 
acid.. 


Sulfo acid of 4-tolyl 1- or 2-amino ANTHRAQUINONE or other alphyl deriv., brominated in 
glac. acetic acid then condensed with 4-roLu1pIN or other primary aromatic amin by refluxing in 
1o parts of the amin, then pptd. by alc. Dark powds. of metallic luster, sol. in hot aq. and alc. 
(B) changing to (GB) with NH, or NaOH, sol. in conc. sulf. (BV) on diln. (G); green BLUE 
acid or BLUE acid mordant (Cr) dyes. 

Note 675,572-3 and -5. 


675,575—June 4, 1901. Robert E. Scumipt and Paul Tust, Germany. (Elberfeld.) 


Anthraquinone dye and process of making same. 1-Amino 4-toluidino anthra- 
quinone sulfo acid and isomers. 


1-Amino 4-oxy ANTHRAQUINONE sulfo, derived from treatment of a and b nitro anthraquinone 
sulfo acids with S,O,, condensed with 4-TOLUIDIN or other primary amin by heating at 150-160° 
with 10 parts of the amin and 0.33 part of boric acid, then pptd. by HCl. Dark powds. sol. in 
aq. in ninety per cent alc., in NH, and fifty per cent acetic acid (B), turned redder by HCl, 
sol. in conc. sulf. (V) on diln. changing to (R) and pptg.; Btu acid or acid mordant (Cr) dyes. 
fast to light and alks. 


682,523—Sept. 10, 1901. Rene Boun, Germany. (Badische.) 


' Blue dye and process of making same. N-Dihydro 1.2-1/2’-dianthraquinone azin or in- 
danthrene, and leuco and sulfo derivs. 


2-Amino ANTHRAQUINONE, its sulfo acid or hydrogenized derivs., fused in 50 parts KOH 
at 250°. Product may be sulfonated to soluble dye, by heating to 50-60° in very dil. NaOH 
soln. containing hydrosulfite. A blue substance insol. in aq. and NaOH, sol. in conc. sulf. 
(YBr), oxidized by CrO,(Y), may be again reduced and is then sol. in NaOH; a sive acid 


or vat dye. 
S. 837—‘Indanthrene Blue R,” and S. 838—‘“Indanthrene Blue RS.” 


24 DIGEST OF PATENTS 


686,356—Nov. 12, 1901. Sigismund E. Srmon, New Jersey. 
Brown anthracene dye and method of making same. _ 1.2.3-Trioxy anthraquinone. 


1.3-Dinitro 2-oxy ANTHRAQUINONE (a) reduced and oxidized by Fe(OH), in alk. soln. to give 
trihydroxyl deriv., or (b) reduced by SnCl, and HCl to the diamino comp., diazotized and boiled 
to convert to hydroxyl groups, or (c) the diamino product treated with HCl or other acid 
under pressure to replace NH, by OH. Reduction must affect only the nitro groups and not 
the carboxyl of the anthraquinone nucleus. A red brown powd., sparingly sol. boiling aq. (OY), 
sol. in alc. (OY), slightly sol. in ether (Y) in CHC1,((GY), in conc. sulf. (Br), pptd. on diln., 
sol. in NaOH or NH,(Br); a fast Brown acid mordant (Cr) dye. 

Probably S. 782—‘‘Anthracene Brown.” 


687,657—Nov. 26, 1901. Robert E. Scumipt and Adolf Srertorius, Germany. (Elberfeld.) 
Green anthraquinone dye and process of making same. 1.s-Ditoluidino dimethyl 

4.8-diamino anthraquinone sulfo acid and other alphyl derivs. 

1.5-Dibrom or dinitro dimethyl 4.8-diamino ANTHRAQUINONE, boiled in 10 parts 4-TOLUIDIN 
or other aromatic amin until uniform in shade, pptd. by alc., then sulfonated. Product treated 
with oxidizing agents gives 1.4.5.8-tetraoxy anthraquinone. Dark green powds., sol. in aq., alc. 
and C,H,N(B), not changed by alk., with acids (V), sol. conc. sulf. (V) on diln. (B), acid soln. 
heated with MnO, then with bisulfite ppts. tetraoxy deriv. (Br); GrEEN acid dyes. 

Note 687,658. 


687,658—Nov. 26, 1901. Robert E. Scumipt and Adolf Srertrorius, Germany. (Elberfeld.) 
Blue anthracene dye and process of making same.  4-Toluidino methyl 1-amino 
anthraquinone sulfo acid or related comp. 
Methyl 1-amino 4-chlor ANTHRAQUINONE or brom or nitro compound, heated at 180° in 
IO parts 4-TOLUIDIN, anilin or other primary amin, pptd. by alc. then sulfonated in 10 parts sulf. 
monohydrate at 50-80°. Dark blue powds., sol. in aq. (GB-B), oxidizable to quinizarin in hot 
acid soln., sol. in conc. sulf. (B) on diln. (R); green BLUE to BLUE acid dyes, fast to light. 


688,57 6—Dec. 10, 1901. Oscar Batty, Germany. (Badische.) 


Green dye of the anthracene series. (Process also claimed.) Anilino toluidino an- 

thraquinone sulfo acids and other alphyl amino derivs. 

1-or 2-Nitro ANTHRAQUINONE sulfo acid and ToLUIDIN or other primary amin condensed to 
toluidino anthraquinone sulfo, halogenated in aq. soln. with 1-4 mols. halogen, condensed with 
ANILIN or other aromatic amin, by heating with excess then sulfonated by warming slightly 
in 20 parts sulf. monohydrate. Products are sol. in aq. (R), in alc. (YR-BrR), in conc. sulf. 
(GBr-Br); RED acid or GREEN (Cr) acid mordant dyes. 

Addition to 656,081. 


688,645—Dec. 10, 1901. Max H. Ister, Germany. (Badische.) 
Dye of the anthracene series and process of making same. Toluidino amino 2- 
methyl anthraquinone sulfo acids. 

Amino 2-methyl ANTHRAQUINONE bromide or other halogen, amino or diamino comp., con- 
densed with 4-TOLUIDIN, using 10 parts of the amin and 1 part sodium acetate or other weak 
alk. salt, pptd. by HCl and sulfonated in usual manner. Sulfonated dye is sol in aq. (VB), in 
conc. sulf. (BV) with boric acid, warmed, (B with R fluor), in C,H;NH, (B); sive acid dyes. 

Note 654,294 and 95, 631,607 and 608. 


690,292—Dec. 31, 1901. Max H. Ister, Germany. . (Badische.) 
Anthraquinone dye and process of making same. Sulfo acids of toluidino hydroxy 
2-methyl anthraquinone, and other alphyl derivs. 

Amino 2-methyl ANTHRAQUINONE, brominated (or chlorinated), treated with nitrite and boiled 
to form brom hydroxy methyl anthraquinone, boiled in 10 parts 4-ToLUIDIN, or other aromatic 
amin, pptd. by alc., then sulfonated in 20 parts monohydrate at 100° or for longer time at 
common temp. ‘The unsulfonated dye is sol. in conc. sulf. (BG) with boric acid (V-B), in 
aniline (BV-B) in alc. (V) and in sulfonated form is sol. in aq. (V) becoming (B) with NaOH, 
sol. in conc. sulf. (RV-B) and redder with boric acid; vioLEr acid dyes. 


692,762—Feb. 4, 1902. Rene Boun, Germany. (Badische.) 
Blue sulfonated dye. Indanthrene mono or disulfo acid. 
2-Amino ANTHRAQUINONE sulfo heated at 150-175° with 2 parts KOH to condense a dye with 


GROUP III.—ANTHRAQUINONE 25 


sulfo group still attached to molecule. Reduced dye is used in vat, the oxidized dye gives greener 
blue shade and sulfonated dye is also valuable. Dye is sol. in aq. (B), in conc. sulf. (BrG), 
in oleum (BrR), in mixed acid (YR)), pptd. from aq. soln. by NaOH (B); in alk. hydrosulfite 
forms BLUE vat dye, when sulfonated is BLuE acid dye which when oxidized with CrO, turns (Y) 
and is green BLUE acid dye. 

Near S. 837—‘“‘Indanthrene Blue mono or disulfo acid.” Note 682,523. 


702,445—June 17, 1902. M. Lance and T. Emitewicz, Netherlands. 
Process of making mordant colors. 1.8-Dioxy naphthalene mono or di-keto derivs. 


1.8-Dioxy NAPHTHALENE, or its acidyl deriv., is condensed with carboxylic acids or their 
anhydrids, with acid chlorides, or bromides, with trichlorides or bromides, by heating with con- 
densing agents such as ZnCl,, SnCl,, Al,Cl,, H,SO,, etc. YELLOW to ORANGE acid mordant dyes. 


704,798—July 15, 1902. Christopher Hartmann, Germany. (Hochst.) 


Blue anthraquinone dye and process of making same. Formaldehyde compound of 
tetra amino anthraquinone. 


1.5- or 1.8-Diamino ANTHRAQUINONE or crude mixture, acetylated, nitrated, and reduced to 
tetra amino anthraquinone, then heated at 25-30° in aq. soln. to hydrolize and condensed with 
FORMALDEHYDE in sulfurous acid or bisulfite. soln. Method of purification is given. Dark blue 
powds., sol. in conc. sulf. (B), in aq. (GB), unchanged by acids or alks; green BLUE acid dyes, 
fast to alk., light and boiling. 


707,3873—Aug. 19, 1902. Oscar Batty, Germany. (Badische.) 


Anthracene dye and process of making same. Sulfanilino comp. of amino anthra- 
quinone sulfo acids, homologs, derivs., and higher sulfonated acids. 


Mono, di, or tri-halogen amino ANTHRAQUINONE sulfo acids or their phenyl derivs., condensed 
with SULFANILIC, metanilic, or other sulfo acid of primary amin by heating at 180—200° in auto- 
clave with alk. or alk. earth salt present to absorb HCl. May be further sulfonated. Large table 
of reactions given. Dyes are sol. in aq., (BG-V), in conc. sulf. alone or with boric acid 
(G-B-V-R); GREEN, BLUE, VIOLET or RED acid mordant (Cr) dyes. 

Note 656,081. 


707,374—Aug. 19, 1902. Oscar Batuy, Germany. (Badische.) 


Anthracene dye and process of making same. 1.8-Disulfanilino anthraquinone or 
other alphyl sulfo derivs. 


1.8-Dinitro ANTHRAQUINONE, isomers and derivs., condensed with suLFANILIC acid, or any 
primary amine derivs. by heating at 200° in autoclave. See table of reactions. Dyes are sol. in 
aq., (RBr-VB), sol in glac. acetic (R-O) in conc. sulf. (YBr-V), RED, BROWN, or BLUE acid 
mordant (Cr) dyes. 


711,310—Oct. 14, 1902. Eduard Hepp, Germany. (Hochst.) 


Polyamidoanthraquinone sulfo-acid and process of making same. _1.4-Diamino 
anthraquinone sulfo acid or the 1.4.5.8 tetra amino deriv. 


r-Amino ANTHRAQUINONE, the 1.5 or 1.8-diamino or crude mixture of alfa amins, acetylated, 
nitrated, saponified by caustic or alk. carb., reduced by Na,S and S and sulfonated. Preferably 
oxamic acid comps. instead of acetyl are formed in the first step by refluxing in 4 parts cryst. 
oxalic acid. Dyes are dark powds., sol. in aq. (BV-B) turning with HCl to (R), sol. in conc. 
sulf. (colorless), alk. solns. turn (R) with zine dust; BLUE acid dyes, fast to light. 

Note 519,229 and 643,451. 


713,432—Nov. 11, 1902. Eduard Hepp, Germany. (Hochst.) 


Process of making polyamidoanthraquinone-sulfo acids. (Product also claimed.) 
Di or tetra alfa amino anthraquinone sulfo acids. 


1.5- or 1.8-Diamino ANTHRAQUINONE or crude reduction product of nitro anthraquinone re- 
fluxed with oxatic acid to form the oxamic acid deriv., as in 711,310, then nitrated, saponified, 
and finally reduced and sulfonated at the same time by refluxing in 8 parts 40° bisulfite. Dark 
blue powds., sol. in aq. (BV-B) turning to (R) and pptg. with HCl, sol. in conc. sulf. (nearly 
colorless), on diln. (V-R), in dil. alk. soln. turns (R) with Zn, but color restored by air; 
blue vioLeT to BLUE acid dyes, fast to light. : 


26 DIGEST OF PATENTS 


715,662—Dec. 9, 1902. Max H. Ister, Germany. (Badische.) 


Anthracene dye and process of making same. Di- or tetra amino di- or tetra- alphyl 
amino 2-methyl anthraquinone sulfo acids. 


2-Methyl ANTHRAQUINONE mono or dinitrated and then reduced with Na,S, is halogenated, 
condensed with 4-ToLUIDIN or other aromatic amin, then sulfonated. The order of adding sub- 
stituents may be varied. Products are soluble in aq. (B), in conc. sulf. (V-VR), in glac. acetic 
(B), insol. in anilin; and are fast BLUE to GREEN acid dyes. 

S. 8s9—‘“‘Cyanthrol R,” and S. 860, ‘“‘Cyanthro]l G.” 


723,125—Mar. 17, 1903. Oscar Batty, Germany. (Badische.) 


Green anthracene dye and process of making same. Di- to poly-alphylamino an- 
thraquinone sulfo acids. 


Nitro ANTHRAQUINONE derivs. condensed with sulfo acids of aromatic amins, halogenated and 
again condensed in an autoclave with an aromatic amin such as 4-TOLUIDIN yielding two prod- 
ucts, A and B, insol. and sol. in alcohol. Product A is sulfonated. (See tables of reactions). 
Products are sol. in aq. (G), in alc. and glac. acetic (B), in conc. sulf. (V-B); GREEN, GRAY, or 
blackish GREEN acid or acid mordant dyes. 


724,789—Apr. 7, 1903. Rene Boun, Germany. (Badische.) 
Blue dye and process of making same. Indanthrene and isomers. 


2-Amino ANTHRAQUINONE fused in 2-5 parts KOH at about 250° with oxidizing agents to pro- 
duce larger proportions of product “A” of 682,523 or heated in KOH below 180° with alcohol to 
produce “B.” Separation of isomeric “‘A” and ‘‘B” described. Dark blue crysts., insol. in aq., 
in NaOH and mineral acids. ‘A’ is diff. sol. in anilin, quinolin and nitrobenzene (B), “B” is 
easily sol. when reduced (BrR); BLUE vat dyes. 

S. 837—‘“‘Indanthrene Blue’’ and S. 850, ‘“‘Indanthrene Blue WB” (probably). Note 682,523 
and 723,125. 


727,389—May 5, 1903. Heinrich LAuBMANN, Germany. (Hoéchst.) 


Blue dye and process of making same. Diamino or dinitro disulfo anthrachrysone di- 
alkyl ethers. 


ANTHRACHRYSONE, Na salt, heated at 100° with equal or double quantity pIMETHYL sulfate to 
form dimethyl ether which is heated with 10 parts fuming sulfuric (twenty per cent anhyd.) 
till easily soluble, cooled, 2 mols. HNO, added and gently heated to form dinitro disulfo deriv. 
that may be reduced in acid or alk. soln. Dark blue cryst. powds., sol, in aq. (B), in conc. 
sulf. (O-Y) on diln. (B); BLUE acid dyes. 


729,073—May 26, 1903. Max KuceEt, Germany. (Elberfeld.) 
Anthracene dye. Sulfonated 4-oxy anthraquinone 1.2-toloxazin, or other. 


1.Toluidino 2’4-dioxy ANTHRAQUINONE or other alfa alphylamino deriv. with ortho-hydroxy 
group, oxidized to an anthraquinone 1.2-TOLOXAZIN, then sulfonated in 2.5 parts fuming sulf. 
(ten per cent $O,) at 7o-80°. Dark powds., sol. in hot aq. (V-GB); BLUE acid or VIOLET to 
GREEN acid mordant (Cr) dyes. 

Note 722,719. 


734,325—July 21, 1903. Otto Hess, Germany. (Héchst.) 
Green anthraquinone dye and process of making same. Probably disulfo 5.8- 
ditoluidino alizarin, etc. : 


1.2.5.8-Tetra-oxy ANTHRAQUINONES, ‘‘Alizarin Bordeaux,’ from 5.8-dinitro 1.2-dioxy anthra- 
quinone condensed with 4-ToLUIDIN or other primary aromatic amin or salts of same. Green 
powds., sol. in aq. (G), in conc. NaOH (BG); GREEN acid or yellow GREEN acid mordant (Cr) 
dyes. 

S. 854—‘“‘Alizarin Viridin DG.” 


734,866—July 28, 1903. Eduard Hepp and Christopher Hartmann, Germany. (Ho6chst.) 
Blue anthraquinone dye and process of iene 2. same. 1-Amino brom 4-toluidino 
anthraquinone 5-sulfo, isomers or poly sulfo deriv. 
Brom 1-amino ANTHRAQUINONE 5- or 8-sulfo or mixture of two heated at 140-150° with 
4-TOLUIDIN or other aromatic amin, product separated by HCl and sulfonated at 20° in 10 


= 


GROUP III.—ANTHRAQUINONE 27 


parts fuming sulf. (three per cent SO,). Dark powds., sol. in aq. (B), not pptd. by NaOH or 
Na,CO,, soln. with HCl (V), sol. in conc. sulf. (Bt), on diln. (R-V) and pptd. (B); sius acid 
or acid mordant (Cr) dyes. 

S. 851—“‘Alizarin Direct Blue B.”’ Addition to 666,594. 


738,614—Sept. 8, 1903. Max H. Ister, Germany. (Badische.) 
Anthracene dye and process of making same. Sulfo methylene comp. of toluidino 

1.5-diamino anthraquinone sulfo acids, the 1.8 or 1.3 isomers and other alkyl amino derivs. 

1.5-, 1.8- or 1.3-Diamino ANTHRAQUINONE sulfo methylene deriv., from 1.5-diamino ANTHRA- 
QUINONE, FORMALDEHYDE and sulfite, brominated, condensed with 4-ToLUIDIN or other primary 
aromatic amin, then sulfonated (see tables of reactions). Products are sol. in aq., in alc., or 
anilin (B-BG), in conc. sulf. (VR) with boric acid (G-BG); BLUE to blue GREEN acid or acid 
mordant (Cr) dyes. 


739,145—Sept. 15, 1903. Rene Bown, Germany. (Badische.) 
Anthracene dye. 1.1’-Di-anthraquinone, united also by two C = N groups between 2.2’-NH, 

and two nearest CO groups. 

2-Amino ANTHRAQUINONE a) fused in KOH at 340° with or without HNO,; 6) or heated 
in anhyd. sublimed Al Cl, at 250—-280° then boiled out with dil. HCl c) or other methods as 
described for mixed a) and b) product, then purified as bisulfite reduction comps. Brownish 
substance, insol. in aq.; YELLOW or GREEN vat (B) dyes. 

S. 849—‘“‘Indantrene Yellow G paste.’”? Note 682,523 for related blue dye. 


739,579—Sept. 22, 1903. Rene Boun, Germany. (Badische.) 
Blue coloring-matter. Dibrom hydro indanthrene. 
2-Amino ANTHRAQUINONE, fused in NaOH, with or without oxidizing agent, hydrogenated and 


Br or Cl derivative formed. Products are BLUE vat dyes, fast to Cl. 
S. 843—“Indanthrene Blue GC.” 


746,405—Dec. 8, 1903. Karl Tuun, Germany. (Elberfeld, New York.) 
Purpurin-alpha-sulfonie acid. Anthrapurpurin 5- or 8-sulfo. 

ANTHRAQUINONE 5- or 8-sulfo heated at 30° in 15 parts fuming sulfuric (eighty per cent 
SO,), separated and boiled in KOH soln. Sodium salt is red powd., sol. in aq. (YR), in NH,, 
NaOH and Na,CO, (R), in conc. sulf. (YR), with boric acid (VR); RED (Al) or violet RED (Cr) 
acid mordant dyes. 


748,375—Dec. 20, 1903. Eduard Hepp and Christoph Hartmann, Germany. (Hoéchst.) 
Blue anthraquinone dye and process of making same. 1-Amino 4-anilino anthra- 

quinone 5-sulfo acids. 

1.5-or 1.8-Amino oxy ANTHRAQUINONE derived by alk. fusion of sulfo acid, brominated, 
separated and condensed with ANILIN, or other primary aromatic amin, then sulfonated. Dark 
blue powd., easily sol. in aq. (B), turning with NaOH or Na,CO, (BV), sol. in conc. sulf. (VB) 
on diln. (R) then pptd; sLug acid mordant (Cr) fast dye. 

Near S. 851—‘“‘Alizarin Direct Blue B.” Addition to 734,866. 


749,913—Jan. 19, 1904. Oscar Batty, Germany. (Badische.) 
Anthraquinone dye and process of making same. Purpurin sulfanilate. 
PuRPURIN, twenty per cent paste, or other hydroxy anthraquinone, heated in aq. soln. with 
one mol. sULFANILIC acid, or other sulfo acid of an aromatic amin. Products are sol. in aq. (R-V) 
with NaOH (more B), sol. in anilin (R-V), in conc. sulf. (R-V) with boric acid (dull B); blue 
VIOLET to blue BLAcK acid mordant (Cr) dyes.. (See table of reactions). 
Near S. 862—‘‘Alizarin Blue Black B.” 


753,657—Mar. 1, 1904. Oscar Batty, Germany. (Badische.) 


Anthracene dye and process of making same. Amino I- or 2-anilino anthraquinone 
sulfo acids, or other alphyl amino derivs. 

1- or 2-Anilino ANTHRAQUINONE sulfo, treated in aq. soln. with bromin or other halogen, 
separated and heated at 200° in autoclave with NH,, or a primary alphyl amin. Products are sol. 
in aq. (BrV), not changed by NaOH or Na,CO,, in conc. sulf. (Br); gray BLUE to blue BLACK 
acid mordant (Cr) dyes. : 

3 ; 


28 DIGEST OF PATENTS 


753,659—Mar. 1, 1904. Rene Boun, Germany. (Badische.) 

Anthracene derivative and process of making same. Dichlor indanthrene. 
INDANTHRENE or product of 682,525, heated at 50° in mixed fuming HNO, and HCl, diluted, 

etc. Product is yellow brown in color, and is a BLUE vat dye, greener than indanthrene and 


fast to Cl. 
S. 842—“‘Indanthrene Blue GCD.” Addition to 739,579. 


754,264—Mar. 8, 1904. Heinrich We.tz, Germany. (Badische.) 
Anthracene dye and process of making same. Alphylamino derivs. of purpurin 
sulfo acid. 


ANTHRAQUINONE 2-sulfo added to ninety-six per cent sulfuric acid containing nitrite and an 
accelerator such as As,O, and mercury sulfate, temp. raised to 210°, and separated product 
heated in autoclave at 160° with ANILIN till soluble in sulfuric with violet color. Other methods, 
reagents and components claimed. Products are sol. in aq., which with NaOH is (B-V), with 
NH, (BV-VR), sol. in conc. sulf. (V), with boric acid (B); BLack acid mordant (Cr) dyes. 


754,768—Mar. 15, 1904. Eduard Hepp and Ernst Wo.upPErtT, Germany. (Hochst.) 
Process of making anthraquinone dyes. (Product claimed.) Poly oxy anthraquinone 

in which two or more hydroxyl groups are replaced by sulfonated aromatic amino radicals. 

1.4.5.8-letra Oxy ANTHRAQUINONE leuco form, heated with equal parts of cryst. boric acid 
and sodium acetate, 7 parts fifty per cent acetic, and 3 parts sodium salt of SULFANILIC acid. 
Other components and reagents are claimed. Dark blue powds., sol. in aq. and NH, (B), pptd. 
by acids, sol. conc. sulf. (B), reduced by Zn and dil. NaOH and restored by air; BLUE acid 
or acid mordant (Cr) dyes. 

S. 865—‘‘Alizarin Cyanin Green E,” or “‘Alizarin Direct Green G.” 


756,57 1—Apr. 5, 1904. Rene Boun, Germany. (Badische.) 


Black dye and process of making same. Sulfo acid or leuco compound or possibly a 
thio sulfonic acid of naphthazarin. 
NAPHTHAZARIN intermediate, prepared as 1n 661,438, melt diluted with ice, filt., and twenty 
per cent thiosulfate added to filtrate until all pptd. Product is sol. in aq. (V), in dil. caustic (G), 
on exposure to air (B), sol. in conc. sulf. (RV); a vioLet acid or green BLACK acid mordant (Cr) 
dye, which when heated with sod. bisulfite and sulfite and printed on cotton, gives green black 
shades. 


763,233—June 21, 1904. Heinrich Weutz, Germany. (Badische.) 
Anthracene dye and process of making same. Amino dioxy anthraquinone sulfo. 


ANTHRAQUINONE 2-sulfo converted to polyoxy sulfo comp. according to 754,264 by cone. 
sulf. with Hg, nitrous and arsenic acids, or other accelerators, and product heated in autoclave at 
120° with 10 parts twenty-five per cent NH,. Product is sol. in hot aq. (RV), which with NaOH 
is (V), with Na,CO, (Rt), sol. in conc. sulf. (OY), in hot anilin (R); a rep acid or violet rED 
(Al) to brown vioLet (Cr) acid mordant dye. 


764,837—July 12, 1904. Wilhelm BercHELMANN, Germany. (Elberfeld.) 
Blue anthraquinone dye. Sulfo acids of methyl 1-amino 4-toluidino 2-methyl anthraqui- 
none, or other. 

Methyl 1-amino 2-methyl ANTHRAQUINONE obtained from nitro methyl ANTHRAQUINONE and 
METHYL amin in pyridin soln. treated with 1 mol. bromin, product refluxed with 10 parts 4- 
TOLUDIN containing sod. acetate, dye separated and sulfonated. Ammonium salts are dark blue 
powds., nearly insol. alc., CHCI,, sol. in hot pyridin (GB), in dil. HCl (R), turned by NH, to 
(B), sol. conc. sulf. (V); BLUE acid dyes. 


767,259—Aug. 9, 1904. Rene Boun, Germany. (Badische.) 
Anthracene dye. Indanthrene derivs. 


1.5-Diamino ANTHRAQUINONE, or the 1.8-, 1.3-, 2.6-, or 2.7- derivs. or sulfo acids, added 
to 3 parts fused KOH at 180°, raised to 190-200°, cooled, diluted, and filt. Gray red to gray 
olive pastes or brown to black powds., insol. in aq.; GRAY vat (Br) dyes. 

S. 848—“Indanthrene Gray B.” Note 682,523 and 739,145. 


a 


GROUP III.—ANTHRAQUINONE 29 


772,857—Oct. 18, 1904. Ludwig Wouman, Germany. (Elberfeld.) 
Trioxyanthraquinone dye. _ 1.2.5-Trioxy anthraquinone. 

Axizarin added at 30-35° to fuming sulf. (eighty per cent SO,) containing boric acid, and 
separated sulfuric acid ester saponified by dissolving in hot dil. NaOH. Red needles m.p. 273- 
274° when cryst. from glac. acetic, tricetyl deriv. yellow needles, m.p. 227-228°, sol. conc. sulf. 
(RV) with boric acid (B), sol. alc. NaOH (B) with special spectrum; a violet rep (Al) or blue 
VIOLET (Cr) acid mordant dye. 


775,367—Nov. 22, 1904. Max Kuce., Germany. (Elberfeld.) 
Green anthracene dye. 4.4’-Diamino 3.3’-dibrom indanthrene. 

1.4-Diamino 2.3-dibrom ANTHRAQUINONE, 2 mols., boiled in nitrobenzene soln. with anhyd. 
sod. acetate and a little CuCl,. Blue black needles, insol. aq., sol. conc. sulf. (G); a GREEN vat 
(B) dye. 

S. 847—“‘Algol Green B.”’ Credited by Schulz to Bayer Co. Note 775,368 and 69. 


775,368—Nov. 22, 1904. Max Kucet, Germany. (Elberfeld.) 


Blue anthracene dye. N-Dimethyl indanthrene. 


1-Methyl 2-brom ANTHRAQUINONE, 2 mols., boiled in nitrobenzene soln. with sodium acetate 
and CuCl,. Blue needles, sol. hot CLH;NO,, C,H;NH, and quinolin (GB), in conc. sulf. (YBr); 
a BLUE vat dye. 

S. 8390—‘‘Algol Blue N.” Addition to 775,367. 


775,369—Nov. 22, 1904. Max Kuce., Germany. (Elberfeld.) 
Green-blue anthraquinone dye. 3.3’-Dibrom indanthrene. 


1.3-Dibrom 2-amino ANTHRAQUINONE, 2 mols. boiled in nitrobenzene soln. with sodium acetate 
and CuCl,. Blue needles, sol. hot C,H;NO, and C,H,NH, (GB), in conc. sulf. (GBr); a green 
BLUE vat dye. 

Note 775,367-68 and 765,121. 


778,036—Dec. 20, 1904. Eduard Hepp and Rudolf UHLENHUTH, Germany. (Hochst.) 
Anthraquinone dye and process of making same. 8-Oxy 1.4-ditoluidino anthra- 
quinone. 


1.4.5-Trioxy ANTHRAQUINONE hydride or other is heated with 4-ToLuIpIN and boric acid, sep- 
arated and sulfonated. Trioxy anthraquinone hydride is derived from nitro ANTHRAQUINONE 
sulfo acid 1.5 and 1.8, changed to methoxy ANTHRAQUINONE sulfo acids by caustic alkali in 
methyl alc. soln. then converted into 1.4.5-trioxy ANTHRAQUINONE by nitration, reduction and 
heating under pressure with lime, the hydride resulting when heated with ZnCl,. Green powds.; 
sol. in aq. (G) not changed by Na,CO,, more (B) with NaOH, sol. conc. sulf. (G); GREEN 
acid and acid mordant (Cr) dyes, fast to light, acid, alks. 


778,670—Dec. 27, 1904. Michael Injinsxy, Germany. 
Ortho-dioxyanthraquinone-sulfo acid and process of making same. 1.5-or 1.8- 

Dioxy anthraquinone sulfo acids. 

ANTHRAQUINONE 1-stlfo acid heated at 180-200° in autoclave with conc. soln. of Ca(OH), 
containing CaCl, and KNO,, the CaCl, or other alk. earth chloride reacts with harmful alkali 
set free in melt, forming alk. chloride and alk. earth hydroxide and the oxidizing agent, which 
may be varied, aids the formation of hydroxy anthraquinone. Products form easily sol. alk. 
salts and diff. sol. alk. earth salts; and are violet rED acid mordant dyes. 


779,825—Jan. 10, 1905. Heinrich Weitz, Germany. (Badische.) 
Anthraquinone dye and process of making same. Sulfo acids of anilino alizarin. 

ANTHRAQUINONE 2-sulfo converted to puRPURIN sulfo by heating in conc. H,SO, with Hg., 
nitrous and arsenic acids, etc., which is then heated in an autoclave at 200-205° with P,O; and 
about 3 parts suLFANILIC acid, Na salt, or other sulfo acid of an aromatic amin. Water and 
condensing agent may or may not be present. Product is sol. in aq. (R), changed by NH, or 
Na,CO, (V), sol. in conc. sulf. (R) with boric acid (VB), sol. hot anilin (V); violet rEp acid or 
violet BLuE (Cr) to viocet (Al) acid mordant dyes. 


785,121—Mar. 21, 1905. Robert E. Scumipt, Germany. (Elberfeld.) 


Greenish-blue anthraquinone dye. 3.3’-Dibrom indanthrene. 


1.3’-Dibrom 2-amino ANTHRAQUINONE condensed in nitrobenzene with CuCl, and sod. acetate 
to form a dibrom INDANTHRENE, which is heated in sulfuric acid to 70-90° with FORMALDEHYDE. 


30 DIGEST OF PATENTS 


Dark blue powd., sol. conc. sulf. (Br G); green BLUE vat dye. 
Note 775,369 and 785,122. 


785,122—Mar. 21, 1905. Robert E. Scumipt, Germany. (Elberfeld.) 
Green-blue anthraquinone dye. Formaldehyde condensed with indanthrene. 


2-Amino ANTHRAQUINONE melted with KOH to form dye of 682,523, then heated in H,SO, 
soln, with FORMALDEHYDE. Dark blue powd., sol. in conc. sulf. (GBr); a green BLUE vat dye. 
Addition to 785,121. 


785,123—Mar. 21, 1905. Robert E. Scumipt, Germany. (Elberfeld.) 
Green anthraquinone dye. Formaldehyde condensed with 4.4’-diamino 3.3/-dibrom anthra- 
quinone. 


1.4-Diamino 2.3-dibrom ANTHRAQUINONE condensed as in 775,367 to form 4.4’-diamino 3.3/- 
dibrom INDANTHRENE, which is heated at 50-80° in conc. sulf. with FoRMALDEHYDE. A dark 
green paste or green black powd., sol. in conc. sulf. (YG); a GREEN vat (VB) dye. 


786,085—Mar. 28, 1905. Oscar Batiy, Germany. (Badische.) 


Violet anthracene dye and process of making same. A complex dye from 
anthraquinone quinolin and two mols. glycerin is condensed to an indanthrene. 


2-Amino ANTHRAQUINONE, or derivs. condensed in H,SO, soln. with 2 mols. GLYCERIN, with 
or without nitroglycerin, He melted with caustic alkali to for dye like indanthrene. Product 
is a VIOLET vat dye. 


787,824—Apr. 18, 1905. Rene Boun, Germany. (Badische.) 
Process of making black dyes. Disulfanilino anthraquinone and isomers, or homologs. 


NAPHTHAZARIN or 1.8-dioxy anthraquinone treated in aq. soln. with boric acid and SuUL- 
FANILIC acid, Na salt, or other sulfo acid of an aromatic amin. Blue BLacK acid mordant (Cr) 
dyes. 

Addition to 631,613 and 661,438. 


787,859—Apr. 18, 1905. Roland H. Scuout, and Oscar Barty, Germany. (Badische.) 


Anthracene compound and process of making same. Benzanthrone or derivs. 


ANTHRACENE, anthranol, or other, heated at 100-110° in fuming H,SO, with cLycrrin (ZnCl, 
can be used for sulf. acid, or fuming HCl in autoclave) then melted with caustic alkali. Products 
are sol. in conc. sulf. (O-G with G-R oh AUPE BLUE vat dyes. 

Note 786,085. 


790,079—May 16, 1905. Robert E. Scuomipt and Arnold Fiscuer, Germany. (Elberfeld.) 
Alizarin dye. 1.2-Dihydroxy benzanthrone quinolin. 

ALIZARIN BLUE or dioxy ANTHRAQUINONE quinolin, which is obtained by action of GLYCERIN 
in sulfuric acid soln. on 2-nitro ALIZARIN, heated with FORMALDEHYDE, in sulfuric acid. A dark 
powd., sol. in conc. sulf. (RBr) or NH, and NaOH (G); Gray to BLack acid mordant (Cr) dye, 
suitable for printing. 

Addition to 775,367. 
791,869—June 6, 1905. Rene Bonn, Germany. (Badische.) 
Brown anthracene dye. Formaldehyde derivs. of indanthrenes. 

I.5- or 1.8-Diamino ANTHRAQUINONE, condensed with FORMALDEHYDE, then heated in caustic 
alkali melt. Black powds., insol. in aq.; BROWN vat (BrR) dyes. 

S. 845—“‘Indanthrene Maroon R.’’ Addition to 767,259. 


793,558—June 27, 1905. Oscar Batty and Hugo Wourr, Germany. (Badische.) 
Anthracene dye and process of making same. Oxy benzanthrone. 


1-Oxy ANTHRAQUINONE or polyoxy or hydro derivs., heated in H,SO, with cLycrrin and 
reducing agent such as ANILIN sulfate. Products are sol. in conc. sulf. (R-Y and GBr fluor), 
in NaOH (YBr with G fluor); yellow Brown (Al) acid mordant dyes. 


796,393—Aug. 1, 1905. Oscar Batty, Germany. (Badische.) ~ 


Anthracene coloring-matter and process of producing the same. Nitro or 
amino deriv. of violanthrene (S. 763). 


BENZANTHRONE quinolin, prepared as in 809,892, by heating a BENZANTHRONE with caustic 
alkali, nitrated, then reduced with Na,S or not. Other methods and components claimed. Dark 


» a 
“a 


GROUP III.—ANTHRAQUINONE 31 


green powds., sol. in conc. sulf. and hot C,H;NO, (GB), insol. in aq. and dil. acids and alks.; 
yellow GREEN vat (GB) dyes. 
S. 765—“Indanthrene Green B.” Note 787,859. 


798,104—Aug. 29, 1905. Max H. Ister, Germany. (Badische.) 
Anthracene compound and process of making same. Benznaphthanthrones, m. p. 
108.2 


NAPHTHANTHRAQUINONE or hydro deriv., suspended in 30 parts eighty-two per cent sulf. 
acid, 1 part each of cLiycERIN and anilin sulfate added, and heated for 30-60 min. at 150°. 
Products are sol. in conc. sulf. (YR with Y fluor); green BLUE vat dyes. 


801,418—Oct. 10, 1905. Paul THomascuHEwsk1, Germany. (Elberfeld.) 
Anthraquinone dye. 4.4’-Dioxy indanthrene. 

4-Amino 1-oxy 3-brom ANTHRAQUINONE from amino oxy compound by bromination, boiled in 
naphthalene soln. with anhyd. sod. acetate and CuCl,. Blue needle crysts. sol. in hot quinolin 


(BG), in conc. sulf. (BrG); a green BLUE vat (B) dye. 
S. 844—‘‘Algol Blue 3 G.” 


806,053—WNov. 28, 1905. Rene Boun, Germany. (Badische.) 
Naphthalene dye and process of making same. Oxy comp. of naphthazarin. 

NAPHTHAZARIN boiled in more than 2 mols. twenty-four per cent NaOH, while passing air, 
until color becomes red, then pptd. by acid. Soluble deriv. is formed with bisulfite. When 
pure forms red needles, sol. in sulf. (R), in C,H;NO,(OR); orange rep acid or red BLack (Cr) 
acid mordant dye. 


808,762—Jan. 2, 1906. Max Kuce., Germany. (Elberfeld.) 
Yellow anthracene dye. 3.3'-Dibrom indanthrene. 

2-Amino 1.3-dibrom ANTHRAQUINONE, heated in nitrobenzene with CuCl, and NaOH at 150°. 
Resulting mixture of blue dye of 875,360 is separated from yellow dye of this patent by soln. in 
conc. H,SO,, cooling and diluting to ppt. yellow dye. A yellow powder, sol. in conc. sulf. 


(YO); a brown YELLOW vat (B) dye. 
Note that patent differs from 775,369 in using caustic instead of alkali salt. 


809,892—Jan. 9, 1906. Oscar Batty and Max H. Ister, Germany. (Badische.) 
Violet dye and process of making same. Indanthrene with two anthraquinone-quinolin 
and an anthraquinone ring. 

2-Amino ANTHRAQUINONE or sulfo derivs., condensed in sulfuric acid with GLYCERIN and 
product melted in 6 parts KOH at 150° then at 225-250°. Products are sol. in conc. sulf. 
(G-B); vioLET vat (B) dyes. 

S. 846—“Indanthrene Dark Blue BT.” Note 786,065, 787,859 and 798,105. 
809,893—Jan. 9, 1906. Oscar Batty and Hugo Wo.rr, Germany. (Badische.) 
Anthracene compound and process of making same. Benzanthrones from alfa 

amino anthraquinones. 

1-Amino ANTHRAQUINONE and one mol. GiycERIN heated to 150-155° in 15 parts eighty-two 
per cent sulfuric acid, to form a benzanthrone. Other alfa amino or diamino derivs. except 1.5 
and 1.8 and alfa amino alizarins, may be used. Brown powds., sol. in conc. sulf. (YBr-Br with 
G fluor); violet BLUE vat dyes when fused with alkali. 

Note 786,085 for same process with beta comp. The 1.5- and 1.8-diamino anthraquinones with 
same treatment yield anthraquinone quinolin. 


~8$09,894—Jan. 9, 1906. Oscar Batty and Hugo Woxrr, Germany. (Badische.) 


Anthracene compound and process of making same. Halogen benzanthrone in- 
danthrene and derivs. 


2-Chlor ANTHRAQUINONE or derivs., and 2 parts each of GLYCERIN and anilin sulfate heated 
to 140° in 25 parts eighty per cent sulf. Other reducing agents are claimed. Green to yellow 
powds., sol. in conc. sulf. (RBr-OY and fluor); vari-coLorED vat dyes when fused in alkali. 


Note 786,085, 787,859, 793,558 and 798,104. 


811,471—Jan. 30, 1906. Oscar Batty and Hugo Worf, Germany. (Badische.) 
Anthracene dye and process of making same. Indanthrene quinolin. 


1-Amino ANTHRAQUINONE heated in H,SO, with GLYCERIN to form 1.2-BENZANTHRONE quinolin, 


22 DIGEST OF PATENTS 


then heated in 5 parts KOH and 4 parts abs. alcohol at 160-230°. Product is sol. in conc. sulf. 
(G); BLUE vat (BV) dye. 
Above is specific claim for generic 809,892. 


812,599—Feb. 13, 1906. Robert E. Scumipt and Karl Tuun, Germany. (Elberfeld.) 
Yellow-green anthraquinone dye. _ 1.4-Ditoluidino 8-oxy 7-sulfo anthraquinone, or other. 


1.4.8-Trioxy ANTHRAQUINONE or other, heated to 130° in 20 parts fuming sulf. (thirty per 
cent SO,) containing equal parts boric acid, till soluble, product heated to 100-120° in 10 
parts 4-TOLUIDIN or other primary aromatic amin containing equal weight SnCl, and 0.5 weight 
boric acid, with access to air, then pptd. by methyl alcohol. Dark green powds., sol. in hot 
aq. (G); GREEN acid or acid mordant (Cr) dyes. 


812,684—Feb. 13, 1906. Re. 12,548—Oct. 23, 1906. 
Robert E. Scumipt, Germany. (Elberfeld.) 


Green anthraquinone dye. Probably disulfo ditoluidino oxy anthraquinone with one sulfo 
group each in side chain and nucleus. 


1.4-Di-toluidino 8-oxy 7-sulfo ANTHRAQUINONE, warmed at 30-50° in 4 parts fuming H,SO, 
(ten to twenty per cent SO,). Green powd., sol. in aq. (G), in conc. sulf. (BG), decomp. by 
SnCl, and HCl to 1.4.8-trioxy anthraquinone sulfo; yellow GREEN acid and acid mordant (Cr) 
dyes. 


8§14,137—Mar. 6, 1906. Max H. Isier, Germany. (Badische.) 


Anthraquinon compound and process of making same. _ 1.2-Dianthraquinonyl amin 
sulfo acids and derivs. 


2-Chlor ANTHRAQUINONE boiled in naphthalene soln. containing anhyd. sod. acetate and 
some CuCl, with 1 mol. 1-amino ANTHRAQUINONE, then heated with toluene to remove naphtha- 
lene. Homologs and derivs. claimed, also alfa chlor. beta amino anthraquinones (reaction not 
so favorable) and other solvents. Heating in fuming sulfuric with or without boric acid, to 130°, 
yields dyes. Unsulfonated comps. are diff. sol. in usual solvents, fairly sol. in anilin and 
C,H,NO,, in conc. sulf. (GB); the sulfonated product is brown RED acid dye. 

S. 824—“‘Algol Orange R.”’ 


818,336—Apr. 17, 1906. Oscar Batty and Hugo Wotrr, Germany. (Badische.) 
Blue dye and process of making same. Benzanthrone indanthrenes and derivs. 


2-Chlor BENZANTHRONE, from 2-chlor ANTHRAQUINONE and GLYCERIN, or deriv., added to 4 
parts KOH and 4 parts abs. alc. at 150° then heated at 180°. Products are sol. in conc. sulf. 
(V-Br); vIoLEeT to blue vat (B-VR) dye. 

Note 786,085, 787,859 and 798,104, and for generic claims see 809,892. 


818,992—Apr. 24, 1906. Oscar Batty and Max H. Ister, Germany. (Badische.) 
Anthracene dye and process of making same. Violanthrene. 


OXANTHRANOL condensed in sulfuric acid with GLYCERIN and product melted at 180° to 240° 
in 5-6 parts KOH. Products contain no nitrogen, are sol. in conc. sulf. (B); vioLet vat (VR) 
dyes. 

S. 763—“‘Indanthrene Dark Blue BO.” Note 786,085, 787,859 and 798,104, and for generic 
claims 809,892. 


820,379—May 8, 1906. Oscar Batty and Max H. Isyer, Germany. (Badische.) 
Anthracene dye and process of making same. Probably homologs of 818,992. 


NAPHTHANTHRAQUINONE condensed in sulfuric acid soln. with GLYCERIN, and acetone soluble _ 
portion of product heated in KOH and alcohol at 150-170°. If fused at 200° in KOH and sod. 
acetate, shade is green. Products are sol. in conc. sulf. (BrG); BLUE to green BLUE vat (RBr) 
dyes. 

Addition to 786,085, etc. 


826,509—July 17, 1906. Michael Inyinsxy, Germany. (Wedekind.) 
Alizarin sulfo-acid and process of making same. Alizarin mono sulfonic acid, dif- 
fering from mono acid derived from sulfuric acid without Hg. 


ALIZARIN slowly heated to 115° in 5 parts fuming H,SO, (twenty per cent SO,) containing 
four-tenths per cent mercury sulfate. Potassium salt is red, sol. in aq. (dark R), giving with 
CuSO, (V); a RED acid mordant (Al or Cr) dye. 

S. 781—“‘Erweco Alizarin Acid Red BS.” 


GROUP III.—ANTHRAQUINONE 33 


826,510—July 17, 1906. Michael Inyinsxky, Germany. (Wedekind.) 
Anthraflavin disulfoniec acid and process of making same. Anthraflavin disulfo 
acid. 


ANTHRAFLAVIC acid heated to 120° in 5 parts fuming sulf. (forty per cent SO,) containing 
ten per cent Hg. The new sulf. acid made by using mercury as catalyst is easily sol. in NaOH 
in excess, its K salt forms yellow powd. of microscopic prisms, not needles, and is sol. in aq. (R) 
which soln. with CuSO, turns deep (Br); a rED acid mordant (Al, Cr, Cu,) dye suitable for 
lakes. 

Note 826,509. 


826,750—July 24, 10906. Robert E. Scumipt, Germany. (Elberfeld.) 
Green anthracene dye. Dinitro anthrarufin disulfo acid derivs. 


Dinitro ANTHRARUFIN disulfo acid in dil. actic acid, to which 2.5 parts Na,S in aq. are 
gradually added, is heated to 90-95°, when dye is pptd. Other sulfides and other organic acids 
are claimed and also neutral bath, in which case product is mixed with diamino deriv. of an- 
thrarufin disulfo acid, which may be removed by soln. in dil. NaOH. Product is dark green 
powd., sol. hot aq. (G), diff. sol. NaOH, sol. in conc. sulf. (YR), with boric acid (VR); a 
GREEN acid dye. 


8§31,002—Sept. 11, 1906. Max H. Ister, Germany. (Badische.) 
Anthracene derivative and process of making same. No claims as to composition 

of products. 

4-Chlor 1-amino 2-methyl ANTHRAQUINONE, one part, nitrated in 10 parts mixed acids then 2 
parts PHENOL added, the product separated and sulfonated. Other 4-halogen 1-amino anthra- 
quinones substituted in the ortho position to the amino group, and other phenols, amines or 
derivs. may be used as second component. Unsulfonated product is insol. in alks; the sulfo 
acids are sol. and form BLUE acid dyes, fast to light, washing, milling, stoving carbonizing, and 
steaming. 


836,220—Nov. 20, 1906. Robert E. Scumipt and Paul Tust, Germany. (Bayer.) 
Yellow anthracene dye. Composition not stated. 


2-Methyl ANTHRAQUINONE heated in 4 parts sulfur at 150-300°, melt dissolved and freed 
from sulfur. Dark yellow cryst. powd., insol. in dil. acids and alks., almost insol. in glac. acetic, 
pyridin, or C,H,NO,, sol. in conc. sulf. (V); a fast yELLOow vat (OBr) dye. 


837,775—Dec. 4, 1906. Oscar Batty, Germany. (Badische.) 
Halogenated dye and process of making same. Halogen violanthrene. 


CYANANTHRENE prepared as in 809,892, or other benzanthrone dye, brominated or chlorinated 
(using sulfur oxy chlorid, halogen vapor, or other halogenizing agent) in glac. acetic, nitro- 
benzol or other indifferent solvent, or suspension agent. Products are sol. in H,SO, (V-Br), in 
hot anilin (G-BV); blue vioLet to violet BLUE vat (B-VR) dyes. 

S. 764—‘“Indanthrene Violet RT.” 


837,840—Dec. 4, 1906. Max. H. Isiter, Germany. (Badische.) 
Anthracene dye and process of making same. Auranthrone. 


2-Methyl ANTHRAQUINONE, or mono or dichlor omega halogen derivs., heated to 150-170° 
in 4 parts alc. and 4 parts KOH. Anhyd. sod. acetate may be substituted for alc. or Ca(OH), 
can be employed in an autoclave at 220°. Methods of application are given. The products 
cryst. from C,H,NO, (Y), are diff. sol. in benzene, alc. and ether; YELLOW vat (RBr) dyes. 

S. 759>—‘‘Anthraflavon G.” 


844,835—Feb. 19, 1907. Karl Tuun, Germany. (Bayer.) 
Anthracene derivative. N-Methyl 4/-tolyl anthraquinoyl azin and derivs. 


4/-Tolyl 1-amino 2-amino ANTHRAQUINONE, 1 part, with 1 part forty per cent FORMALDEHYDE 
heated to 100° in 10 parts glac. acetic. Other amino aryl amino anthraquinones, with the amino 
group in ortho position to the aryl amino, and other aldehydes are claimed. Dark cryst. powds., 
insol. in aq. unless sulfonated; sulfo derivs. are BLUE acid dyes. 


844,914—Feb. 19, 1907. Rene Boun, Germany. (Badische.) 
Process of making an anthracene dye. Halogen indanthrene faster to Cl than 739,579. 
INDANTHRENE treated with Sb,Cl, in nitro benzene solution to form chlor derivatives. BLuE 


34 DIGEST OF PATENTS 


vat dyes (properties not claimed), fast to Cl. 
Note 753,659. 


847,078—Mar. 12, 1907. Michael Inyinsxy, Germany. (Wedekind.) 


Production of organic sulfonic acids. Poly sulfo acids of anthraquinone, containing 
one sulfo group in the (1), position. 


ANTHRAQUINONE 2.6- or 2.7-disulfo acid, sodium salt, heated at 160° in 2 parts fuming sulf. 
(forty per cent SO,), containing one per cent HgSO,. Melting with lime yields an oxy an- 
thraquinone sulfo acid which is a violet RED acid mordant dye. 


853,041—May 7, 1907. Paul THoMAsScHEWSKI, Germany. (Badische.) 
Anthraquinone derivative. Methyl anthra-pyridone and derivs. 


Methyl 1-amino ANTHRAQUINONE, the para nitro, para methoxy, or other alfa aryl amino an- 
thraquinone, boiled with acrric anhyd. to form acetyl deriv., then condensed by boiling in 50 
parts alkali, separated and sulfonated by heating gently with 20 parts monohydrate acid. A 
table of reactions is given. Prods. are cryst., insol. in aq., sol. in pyridin, and in conc. sulf. 
(Y-R), the sulfonated products are sol. in dil. alk. (VR); and are violet RED acid or acid mordant 
(Cr) dyes. 

Note 875,390. 


855,248—May 28, 1907. Max IsiterR, Germany. (Badische.) 
Process of making anthracene dye. Indanthrene by another process. 

1-Amino ANTHRAQUINONE one part heated with 1 part twenty to thirty per cent HCl or 
other condensing agent (acids and salts enumerated) with or without oxidizing substance, either 
dry or in condensed or dil. soln., to form an azin. A BLUE vat dye. 

Probably S. 837—“‘‘Indanthrene Blue R.” Note 682,523 for alkali condensation, and also 
724,789. 


856,811—June 11, 1907. Roland H. Scuont, Germany. (Badische.) 
Dye of the anthraquinone series and process of making same. Pyranthrene and 
derivs. 


Halogen 2-methyl ANTHRAQUINONE or derivs., condensed, using copper or other metal capable 
of withdrawing halogen, to 2.2’-dimethyl 1.1’-dianthraquinonyl comp. then refluxed in methyl or 
ethyl alcohol with KOH or other condensing agent to, further condense to a pyranthrone which 
is oxidized by air to pyranthrene. Yellow to brown powds., insol. in aq. and dil. acids and aiks., 
sol. in conc. sulf. (B) and in hot C,H,NO, and C,H;NH,; YELLOW to ORANGE vat (R) dyes. 

S. 760—‘‘Indanthrene Gold Orange G.’’ Addition to 828,778. 


860,480—July 16, 1907. Max IsuerR, Germany. (Badische.) 
Anthracene dye and process of making same. Probably an indanthrene. 


1-Amino ANTHRAQUINONE and 2-chlor ANTHRAQUINONE condensed to 1.2/-DIANTHRAQUINONYL- 
AMIN, nitrated in 20 parts nitrobenzene soln. by 1 part ninety-three per cent HNO, to dinitro- 
dianthraquinonylamin which is melted at 100° in 5 parts Na,S. Blue powd. or paste, insol. in 
aq., dil. acids and alks., sol. in conc. sulf. (GBr) pptd. on diln. (B); BLUE vat dye. 

Addition to 814,137. 


863,397—Aug. 13, 1907. Max Ister and Philip: Kacrer, Germany. (Badische.) 


Anthraquinone compound and process of making same. 2/.2’/-Dianthraquinonyl 
1.5-diamino anthraquinone, isomers and derivs. 


1.5-Diamino ANTHRAQUINONES, or isomers, derived from nitro comp., refluxed with 2 mols. 
2-chlor ANTHRAQUINONE or other beta halogen comp. in 20 parts naphthalene, toluene or nitro- 
benzene, containing anhyd. sod. acetate and Cu,Cl,. Products are insol. in aq., dil. acids and alks., 
diff. sol. in organic solvents, sol. in conc. sulf. (G), bluer on heating; rED vat (R-Br) dyes, or 
in sulfonated form are green GRAY and RED acid dyes as fast to acids, alks., Cl and light as 


vat dye. 

S. 826—‘Indanthrene Red G,”’ S. 828, “Indanthrene Bordeaux B,” S. 830, “‘Indanthrene 
Red R.” Schulz uses the formula 1’.1”%-dianthraquinonyl 2.6-diamino-anthraquinone. 
863,401—Aug. 3, 1907. Filip Kacer, Germany. (Badische.) 


Anthracene dye and process of making same. 4.4’-Diamino 1.1’-dianthraquinone or 
halogen deriv. 


Acetyl 1-amino ANTHRAQUINONE, or halogen deriv., refluxed with POCI,, etc., and separated 


@ 


eigenen is 


GROUP III.—ANTHRAQUINONE 35 


halogen product condensed in nitrobenzene, acetic anhydrid, alcohol, naphthalene, etc., using 
cuprous, aluminum or ferric chloride as condensing agents. Products are insol. in caustic, sol. 
in conc. sulf. (R-BrR); slur vat (YBr) dyes, blue color being developed with neutral hydro- 
sulfite. 


868,399—Oct. 15, 1907. Rene Boun, Germany. (Badische.) 
Anthracene dye and process of making same. Probably a poly oxy dianthraquinone 
xanthone. 


Hexaoxy ANTHRAQUINONE (Anthracene Blue WR ext.) or other oxy anthraquinone heated 
in alk. sulfite with FORMALDEHYDE, then pptd. by acid. Products are sol. in aq. (BR-YBr), in 
dil. NaOH (VR-RBr), in conc. sulf. (OR-V), on diln. (R-YG); violet BLUE to red BROWN acid 
mordant (Cr) dyes. 


8$74,743—Dec. 24, 1907. Joseph Drinet, Germany. (Bayer.) 
Anthracene dye. Probably a dianthraquinone. 


_ANTHRAQUINONE, heated with powd. copper or other metal and 20 parts 66° sulfuric acid 
to 100-120°. A black paste diff. sol. in organic solvents, in conc. sulf. (dull Br); a Brown 
vat (dull V) dye. 

S. 872—“Leucol Brown B.” Note 874,744, and also that Schulz gives different materials and 
method. 


874,744—Dec. 24, 1907. Joseph Dertnet, Germany. (Bayer.) 
Anthracene dye. Probably dimethyl 1.1’-diamino dianthraquinone or N-dimethyl indanthrene. 


Methyl 1-amino ANTHRAQUINONE heated at 90-100° with aluminum bronze (or copper, silver 
or the like) in 20 parts 66° sulfuric acid. Green black paste diff. sol. in conc. sulf. (dull V); 
olive GREEN vat (R) dye. 

S. 866—“‘Leucol Dark Brown B.” Addition to 874,743. 


875,390—Dec. 31, 1907. Paul THoMASCHEWSKI, Germany. (Bayer.) 


Anthraquinone derivative. 2-Anthraquinonyl N-methyl 1-anthrapyridonyl amin or di-1.1’- 
anthrapyridonyl amin. 


Acetyl methyl 1-amino 4-brom ANTHRAQUINONE treated with alkali to form 4-brom anthra 
pyridone, which is condensed with 1 mol. 2-amino ANTHRAQUINONE by heating in naphthalene 
soln. with Ca(OH), and Cu,Cl,. See list of reactions for other components, Method for 
dyeing in vat given in detail. Dark brown powds., sol. in hot quinolin (R) and conc. sulf.(V);- 
RED tO BLUE vat dyes or as sulfo derivs. RED to BLLUE acid dyes. 

S. 825—‘“‘Algol Red B.” Addition to 853,041. 


876,190—Jan. 7, 1908. Max H. Isuer, Germany. (Badische.) 
Anthracene dye and process of making same. Probably an indanthrene nucleus. 


1- or 2-Amino ANTHRAQUINONE or derivs., heated at 90° in sixty per cent sulfuric acid with 
powd. copper or other metal. Products are insol. in aq. and caustic, sol. in conc. sulf. (GBr-RBr) 
not changed by boric acid, sol. in seventy-eight per cent HNO, (YBr-RBr); brown GREEN to 
BROWN vat (BrV-V) dyes. 

S. 867—“Indanthrene Brown B.”’ 


876,810—Jan. 14, 1908. . Max. A. Kunz, Germany. (Badische.) 
Anthracene dye and process of making same. Halogen pyranthrones. 


2.2’-Dimethyl 1.1/-DIANTHRAQUINONYL, or similar comp., heated with alc. KOH in nitrobenzene 
asin 299,775, and product heated at 60—-70° with sulfuryl chloride, Cl gas, or other halogenizing 
agent in nitrobenzene soln. then pptd. by alc. Yellow to brown powds., insol. in aq., dil. acids 
and alks., sol. in conc. sulf., in hot C,H,NH, and C,H,;NO,; orange rED vat (VR) dyes. 
Addition to 299,775. 


885,577—Apr. 21, 1908. Johann H. Boner, Germany. (Badische.) 
Process of making alizarin. Dioxy anthraquinone. 

ANTHRAQUINONE heated at about 200° in mixed NaOH and KOH soln. with KCIO, or other 
oxidizing agent, dissolved in aq. and air blown through to reconvert oxanthrol present to anthra- 
quinone and alizarin, pptd. by Ca(OH),, purified, etc.; a RED acid mordant dye. 

S. 778—‘‘Alizarin.” 


30 DIGEST OF PATENTS 


893,412—July 14, 1908. Hugo Wourr, Germany. (Badische.) 
Anthracene dye and process of making same. Benzanthrone indanthrene and derivs. 


Amino BENZANTHRONE (from nitro compound), heated in nitrobenzene soln. with anhyd. 
sod. acetate and a metallic salt or oxide such as Cu,Cl, as condensing agent. Brom, di and tri 
amino, and quinolin derivs., etc., also claimed. Products are insol. in aq., in dil. acids and alks., 
diff. sol. in quinolin (Br-BrR), sol. in conc. sulf. (RBr-VB); yELLow, RED to violet BROWN vat 
(BrGr-BrR) dyes. 


893,508—July 14, 1908. Max H. Ister, Germany. (Badische.) 
Anthracene dye and process of making same. Probably indanthrene derivs. 


4.4’-Diamino 1.1/-DIANTHRAQUINONYL amin, the dinitro compound of 860,480, or any dianthra- 
quinone compound united by an imino group having an amino group in ortho position to a car- 
bonyl group, heated in fuming sulf. with glac. acetic, or with acetic anhyd. and sulfur when 
nitro comps. are used. Products are insol. in aq., and alk., diff. sol. in alc., glac. acetic, and 
acetone, sol. boiling C,H,;NO, and quinolin; pLuE vat dyes. 

Note 860,480. 


893,837—July 21, 1908. Joseph Drinet, Germany. (Bayer.) 
Green anthracene dye. Probably an oxy indanthrene. 


INDANTHRENE of 682,523, 1 part, in 15 partS NITROBENZENE to which 1 part ninety-five per 
cent HNO, is added, held at ordinary temp. for several hours, then heated to 60-65° for 0.5 hour. 
Gray green powd., sol. in cone. sulf. (YBr) pptd. on diln. (G); GREEN vat (B) dye. 


902,895—Nov. 3, 1908. Bertram Mayer and Alfred ScHaarscHmip?, Switzerland. (Basle.) 


Orange-to-yellow vat dye and process of making same. Composition not in- 
dicated. 


w-Dichlor 2-methyl] ANTHRAQUINONE, the mono chlor deriv., the crude mixture of both, or 
other, is heated with 0.3 to 3.0 parts sulfur at 200-290° for 3-4 hours; melt freed of sulfur by 
extraction with CS, or aq. Na,S, aq. paste of product heated to 100° and NaOCl added. Yellow 
to orange powds., sol. conc. sulf. (BR-RV), in fuming acid (BkG), slightly sol. in organic sol- 
vents; ORANGE tO YELLOW vat (RBr-VBr) dyes, fast to washing, light and chlorine. 

S. 795—‘“‘Cibanone Yellow R.” 


906,367—Dec. 8, 1908. Oscar Baty and Hugo Wo.rr, Germany. (Badische.) 
Anthracene dye and process of making same. (Process not claimed.) Iso violan- 
throne and derivs. 


Chlor BENZANTHRONE, or other halogen deriv., (prepared as in F. P. 6,719, ninth addition 
to 349,531), heated at 150° with potassium or sodium alcoholate. Products are sol. in conc. 
sulf. (G), in C,H;NO, (RV); red vioLET to BLUE vat (B) dyes. 

S. 766—‘‘Indanthrene Violet R.”? Note 809,894 and 818,336 for isomeric comps. 


909,800—Jan. 12, 1900. Max H. Ister, Germany. (Badische.) 
Anthracene dye and process of making same. Probably an indanthrene. 


2-Amino ANTHRAQUINONE heated at 250-280° in 10 parts nitrobenzene with equal weight 
AICI,,. Products are insol. in aq., in NaOH, in alc., sol. in sulf. (BBk-GBk), partly sol. in 
C,H,NO, (YBr-GBk); red Brown vat (RBr-YBr) dyes. Product differs from that obtained in 
absence of a solvent. 


915,385—Mar. 16, 1909. Alfred ScHAARSCHMID?T and Bertram Mayer, Switzerland. (Basle.) 
Brown vat dye and process of making same. Probably an indanthrene thiazin. 
1-Amino 2-methyl ANTHRAQUINONE or other amino, or alkyl or acidyl deriv., heated to 240- 
280° with 3 parts sulfur. Dark brown to black powds., sol. in conc. sulf. (Br-VBr), insol. in 
alc., glac. acetic, and C,H,; yellow Brown to violet BROWN vat (Br-V) dyes, fast to washing and 
light. 
S. 868—‘“‘Cibanon Brown B.” 


916,154—Mar. 23, 1909. Julius HorFMANnNn, Switzerland. (Basle.) 


Gray vat dye and process of making same. Phenyl derivs. of indanthrene thiazin. 


Phenyl amino 2-methyl ANTHRAQUINONE or other aryl amino deriv., heated in 3 parts S. at 
280-290°. Black powds., sol. in conc. sulf. (GBk-BrG) in twenty-four per cent oleum (BrG-Bk), 
insol. in organic solvents; GRAY vat (Br) dyes. 


ieee mel 


GROUP III.—ANTHRAQUINONE 37 


922,282—May 18, 1900. Max IsiErR, Germany. (Badische.) 
Anthracene dye and process of making same. Composition not shown. 


ANTHRACENE, or a non oxidized substitution comp. such as the di or tri-chlor, chlor-brom, 
methyl or amino deriv., is heated at 250-360° with 3 parts sulfur until evolution of H,S ceases. 
Prods. are insol. in aq., in alks., in dil. acids and common organic solvents; and are green 
YELLOW to BROWN vat (Br-B) dyes. 

S. 791—‘Indanthrene Olive G.” 


925,917—June 22, 19009. Filip Kacer, Germany. (Badische.) 


Compound of the anthracene series and process of making same. Probably 
anthrapyridone derivs. 


Acetyl 1-amino ANTHRAQUINONE or other acetyl or diacetyl diamino deriv., refluxed with 2 
parts POCI, or other halogenating comp., such as sulfuryl chloride, etc., as reagent. Products 
which are weak bases, are light brown to red powds., insol. in aq., dil. acids or alks., diff. sol. 
in organic solvents, sol. in conc. sulf. (R), unchanged at 70°; orange RED, BROWN to YELLOW vat 
dyes. 

S. 812—“‘Indanthrene Orange RT,” and S. 813, “Indanthrene Copper R.” 


928,891—July 20, 1909. Paul THOMASCHEWSKI, Germany. (Bayer.) 
Wat dye. 2’-Anthraquinonyl 4-anthriminonyl amin. 

1-Nitro 4-amino ANTHRAQUINONE condensed with 2-chlor ANTHRAQUINONE and reduced to 
form 2/-anthraquinonyl 1.4-diamino ANTHRAQUINONE, which is condensed with vurREa in phenol 
soln. Dark red cryst. powd., diff. sol. organic solvents, sol. conc. sulf. (VB); fast violet RED 
vat dye. 


929,442—July 27, 1909. Max H. Isier, Germany. (Badische.) 
Anthracene dye and process of making same. Halogen pyranthrones. 


3- or 4-Chlor PHTHALIC anhyd., condensed with TOLUENE by Friedel-Crafts reaction and re- 
sulting chlor methyl deriv. nitrated, reduced, diazotized, and treated with Cu, to form 6.6’- 
dichlor 2.2’-dimethyl 1.1/-DIANTHRAQUINONYL, or 7.7’ deriv., which is refluxed in alc. KOH. Halo- 
gen is not lost in reaction. Yellow to brown powds., insol. in aq., acids., alks., sol. in conc. 
sulf., hot C,H,NO, and C,H,.NH, (R); orange RED vat (VR) dyes. 

Addition to 856,811 and 876,810. 


929,443—July 27, 1909. Max H. Isier, Hugo Worrfr and Filip Kacrer, Germany. (Badische.) 
Anthracene dye and process of making same. alfa-beta-Dianthraquinonyl imines 
with two ketonic groups of each anthraquinone intact, and at least one anthraquinone having 

a nonreactive substituent. 

Methyl 1-amino 6- or 7-chlor ANTHRAQUINONE, or other beta chlor deriv., condensed with 1- 
amino ANTHRAQUINONE, or other alfa amino deriv. by boiling in nitrobenzene soln. with CuO 
and calcined soda, etc. Products are sol. in cold conc. sulf. (BrR-VB) containing boric acid, 
when heated (R-B); RED to violet BROWN vat dyes. 

Note 814,137. 


931,618—Aug. 17, 1909. Filip Kacrer, Germany. (Badische.) 


Anthracene dye and process of making same. 2’-Anthraquinonyl 2-methyl 1-an- 
thrapyridonyl imin, and derivs. 


4-Amino 2-methyl ANTHRAPYRIDONE, refluxed in nitrobenzene soln. with 2-chlor ANTHRAQUI- 
NONE, using CuCl, and anhyd. sod. acetate. Other components claimed. Products are insol. in aq., 
acids, alks., alc., and C,H,, sol. in C,H;NO, and quinolin, and conc. sulf. (V); RED vat dyes. 


932,290—<Aug. 24, 1909. Filip Kacrer, Germany. (Badische.) 
Compound of the anthracene series and process of making same. 4/-Toluidine 
2-methyl anthrapyridone. 


4-Chlor 2-methyl ANTHRAQUINONE or other 4-halogen 2-substituted deriv., refluxed in 8 parts 
4-TOLUIDIN, or other aromatic amin, containing anhyd. sod. acetate, pptd. by alcohol, separated 
and sulfonated. Products are sol. in aq. (VR-RV), insol. in alc., ether, C,H,, glac. acetic, sol. 
in conc. sulf. (YR-R), unchanged by boric acid; rEp acid dyes. 
935,590—Sept. 28, 1909. Joseph Drinret, Germany. (Bayer.) 
Vat dye. Dibenzoyl 4.8-diamino anthrarufin. 

4.8-Diamino ANTHRARUFIN boiled in 10 parts nitrobenzene with 4 parts BENZOYL chloride. 


38 DIGEST OF PATENTS 


Dark powd. sol. in pyridin (V), in conc. sulf. (Br), with boric acid (BG); sLrug vat (OR) dye. 
Note 935,781. : 


935,781 Oct. 5, 1909. Joseph Deinet, Germany. (Bayer.) 
Vat dye. Dibenzoyl 1.5-diamino 8-oxy anthraquinone. 
1.5-Diamino 8-oxy ANTHRAQUINONE, boiled in nitrobenzene with BENzoy1 chloride. A red 


powd. sol. in pyridin (R), sol. in small quantity conc. sulf. (BGy) in more sulf. (R); a violet 


RED vat dye. 
S. 819—“‘Algol Red R.” Addition to 935,590. 


935,827—Oct. 5, 1909. Paul THomascuHEwsk1, Germany. (Bayer.) 
Vat dye. Oxy naphthoyl 1-amino anthraquinone, isomers or derivs. 

1-Amino ANTHRAQUINONE or other atnino deriv., heated to 125° in nitrobenzene soln. with 
equal weight 2-NAPHTHOL 3-carbo or other naphthol carbo acid and some SOCI,. Colored powds., 
insol. in aq., sol. in conc. sulf, (R-Br-BrG); yYEILowW to RED to BROWN to VIOLET vat (O-R-Br) 
dyes. 


935,878—Oct. 5, 1909. Ludwig Wouiman, Germany. (Bayer.) 
Vat dye. 2’-Anthraquinonyl 1-amino anthraquinones. 
ANTHRAQUINONE 2-carbo acid or other carbo deriv., heated to 140° with SOCI, in nitro- 


benzene soln. with 1-amino ANTHRAQUINONE, or other amino deriv. Colored powds., insol. in aq., 
sol. in pyridin and conc. sulf. (Y-R); YELLOW, orange RED to BROWN vat dyes. 


938,565—Nov. 2, 1900. Paul Fiscuer, Germany. (Bayer.) 
Vat dye. Dicarboxylic acids substituted by two mols. of an amino anthraquinone. 

1-Amino ANTHRAQUINONE, two mols., boiled in nitrobenzene soln. with one mol. apipic acid 
or other dicarbo acid, with or without PCl,, or other condenser. Other components enumerated 
and method of dyeing described. Colored powds., insol. in aq. and organic solvents., sol. in conc. 
sulf. (Y-R); YELLOW to RED to VIOLET to BROWN vat (OR-V) dyes, suitable for printing. 

Note 938,566. 


938,566—Nov. 2, 1909. Paul Fiscuer, Germany. (Bayer.) 
Yellow dye. 1.1’-Dianthraquinonyl di-succinimid. 

1-Amino ANTHRAQUINONE, two mols., condensed by boiling in nitrobenzene with one mol. 
succinic acid and a condensing agent. List of other components given and dyeing process de- 
scribed. Colored powds., insol. in aq. and organic solvents, sol. conc. sulf. (Y-R); YELLOW to 


VIOLET to BROWN vat (Y-R) dyes. 
S. 811—“‘Algol Yellow 3G.”’ Addition to 938,565. 


938,618—Nov. 2, 1909. Joseph Deringer, Germany. (Bayer.) 
Vat coloring-matter. Dibenzoyl 1.5-diamino anthraquinone. 

1.5-Diamino ANTHRAQUINONE, boiled in 10 parts nitrobenzene with 4 parts BENzoyL chloride. 
Orange powd., sol. in pyridin (Y), in conc. sulf. (R); an orange YELLOW vat (VR) dye. 


Note 938,619, 957,039-40-41-42, 957,125, 957,146, and among “Applications,” see 938,616-17, 
and 972,066. 


938,619—Nov. 2, 19009. Joseph Derrtnet, Germany. (Bayer.) 
Vat coloring-matter. Dibenzoyl 1.8-diamino anthraquinone. 
1.8-Diamino ANTHRAQUINONE, boiled in 10 parts nitrobenzene with 4 parts BENzoyL chloride. 


An orange powd., sol. in pyridin (O), in conc. sulf. (OY); an orange YELLOW vat (BrR) dye. 
Note 938,616 and references. 


941,320—Nov. 23, 19009. 
Max Isxer, Arthur Lurrrincuaus, and Heinrich von Dizspacu, Germany. (Badische.) 
Halogenated naphthanthraquinon and process of making same. 2-Chlor naph- 
thanthraquinone or other halogen derivs. 
2-Chlor PHTHALIC anhyd. or deriv., condensed in nitrobenzene soln. with NAPHTHALENE, or 
deriv., using AICl,, to form chlor benzoyl NapHrHorc acid, which is heated at 55° with 8 parts 


ninety-seven per cent sulfuric acid. Yellow powds., insol. in aq., sol. in conc. sulf. (RBr-G); 
YELLOW vat (BrR-R) dyes, fast to light and suitable for lakes and printing. 


I< e 


Nel 


GROUP III.—ANTHRAQUINONE 39 


943,717—Dec. 21, 1900. ' Rudolf Untenuutu, Germany. (Héchst.) 


Brown anthraquinone dye and process of making same, 1’.1/’-Dianthraquinony] 
1.4-diamino ANTHRAQUINONE. 


1.4-Diamino ANTHRAQUINONE and two mols. 1-chlor ANTHRAQUINONE, heated at 180—210° in 
KOH. Dark powds., insol. in aq., alks, and acids, little sol. in organic solvents, sol. in conc. 
sulf. (Br), pptd. on diln. (Br); Brown vat dyes, fast to light, alks. and Cl. 

S. 873—“‘Helindon Brown AN.” 


948,204—Feb. 1, 1910. Rene Boun, Germany. (Badische.) 
Indanthrene monosulfonic acid and process of making same. Indanthrene mono 
sulfo acid. 


INDANTHRENE BLUE (1.1/-dianthraquinonyl azin) dissolved at 30° in 5 parts sulf. monohydrate 
containing boric acid, more acid added and heated at 130°. Product is diff. sol. in aq. (VB), in 
cone. sulf. (GBr), in twenty-three per cent oleum (GBr); BLUE vat dyes. 

S. 841—“Indanthrene Blue 2GS,” (probably.) Sulfonation with fuming acids yields the di- 
sulfo deriv. of 692,762. 


950,343—Feb. 22, 1910. Heinrich RarpErR, Germany. (Bayer.) 
Vat dye of anthracene series. 4-Methoxy 1.2’-dianthraquinonyl amin. 


4-Amino 1-methoxy ANTHRAQUINONE, condensed with equal parts 2-chlor ANTHRAQUINONE, by 
boiling in naphthalene soln. containing CuCl, and anhyd. sod. acetate. A list of other components 
is claimed. Colored powds., insol. in aq. and organic solvents, sol. conc. sulf. (B-G); RED to 
VIOLET vat dyes (Br). 


950,344—Feb. 22, 1910. Heinrich RarpEer, Germany. (Bayer.) 
Vat dye. 4’.4”-Dimethoxy 1/.1”-dianthraquinonyl 2.7-diamino anthraquinone.. 


1-Amino 4-methoxy ANTHRAQUINONE, or other para amino alkoxy derivs., 2 mols. condensed 
with 1 mol. of a dihalogen anthraquinone, such as 2.7-dichlor ANTHRAQUINONE, by heating in 
naphthalene soln. with CuCl, and anhyd. sod. acetate. Colored powds., insol in aq., and organic 
solvents, sol. in conc. sulf. (B-G); RED to VIOLET vat (Br) dyes. 

S. 8290—‘‘Algol Bordeaux 3B.’”’ Schulz gives the 2.6 deriv. 


955,105—Apr. 12, 1910. Roland Scuott and Max H. Ister, Germany. (Badische.) 

Anthracene dye and process of making. Dibrom or dichlor pyranthrone. 
2.2’-Dimethyl 1.1/-DIANTHRAQUINONYL, condensed with SO,Cl, to form PYRANTHRONE and 

dihalogenated in nitrobenzene soln. Brown powd., insol. in aq., acids, alks., sol. in conc. sulf. 


(B); orange RED vat (VR) dyes. 
'  §. 761—“Indanthrene Gold Orange R,” S. 762, ‘“Indanthrene Scarlet G.” Addition to 


876,810. 
957,039—May 3, 1910. Joseph DeinET, Germany. (Bayer.) 
Vat dye. Benzoyl 1-amino 4-methoxy anthraquinone. 

1-Amino 4-methoxy ANTHRAQUINONE, heated in nitrobenzene with sENzoyy chloride. An 


orange red powd., sol. in pyridin (Y), in conc. sulf. (Br); a rep vat (O) dye. 
Note references under 938,618. 


957,040—May 3, 1910. Joseph Derinet, Germany. (Bayer.) 
Orange wat dye. ‘Tribenzoyl 1.2.4-triamino anthraquinone and isomers. 

1.2.4-Triamino ANTHRAQUINONE or other triamino deriv., condensed with three mols. 
BENZOYL chloride. Colored powds., insol. in aq., sol. in conc. sulf. (Y-R); YELLOW to RED to 


BROWN vat (O-R) dyes, suitable for lakes and printing. 
S. 822—“Algol Brill. Orange FR.” Note 938,618. 


957,041—May 3, 1910. Joseph Drinet, Germany. (Bayer.) 


Vat dye. Benzoyl 1-amino anthraquinone. 

1-Amino ANTHRAQUINONE or other amino anthraquinone, condensed with BENZoyYL chloride 
in nitrobenzene soln. Colored powds., insol. in aq., sol. in conc. sulf. (Y-R-V-Br); YELLOW 
to RED to VIOLET to BROWN vat (O-R-Br) dyes. 

S. 821—‘‘Algol Brilliant Violet 2B.,” S. 822 and 823. Note 938,618. 


40 DIGEST OF PATENTS 


957,042—May 3, toro. Joseph Drerinet, Germany. (Bayer.) 
Vat dye. Dibenzoyl 1.4-diamino anthraquinone and isomers (see list with colors produced.) 

1.4-Diamino ANTHRAQUINONE or other diamino deriv., condensed with 2 mols. BENZOYL 
chloride by heating in nitrobenzene. Colored powds. insol. in aq., sol. in conc. sulf. (various); 


YELLOW to RED tO VIOLET or BROWN vat (O-R-Br) dyes. 
S. 821—“‘Algol Brilliant Violet 2B,” also S. 821 and 823. Note 938,618 et seq. 


957,125 May 3, 1910. Paul THomascHEwsk1, Germany. (Bayer.) 
Vat dye. 2/-Oxy benzoyl 1-amino anthraquinone, isomers and derivs. 

1-Amino ANTHRAQUINONE or isomer, condensed with 1 mol. sanicynic acid, by heating in 
nitrobenzene soln. to 125° with thionyl chloride. List of other components with colors pro- 
duced is given. Colored powds., insol. in aq., sol. in conc. sulf. (Y-R-Br); YELLOW to RED 
to BROWN vat (O-R-Br) dyes. 

Addition to 957,039. 


957,146—May 3, 1910. Joseph Deinet, Germany. (Bayer.) 
Vat dye. Benzoyl 1-amino 4-oxy anthraquinone. 

1-Amino 4-oxy ANTHRAQUINONE, condensed in boiling nitrobenzene with senzoyt chloride. 
Red powd. sol. in pyridin (YR), in conc. sulf. (R); violet rep vat (OR) dye. 

Addition to 957,039. 


958,325—May 17, 1910. Albrecht Scumipt and Georg KRANZLEIN, Germany. (Hochst.) 
Urea of the anthraquinone series and process of making same. Dianthra- 

quinonyl ureas. 

2-Amino ANTHRAQUINONE or Other beta amino deriv. is condensed a) with rEtuyyt chlor 
carbonate to form 2-ANTHRAQUINONYL urethane or b) with PHOSGENE in nitrobenzene soln. to 
form the urea chloride, and either a) or b) is heated to 250° with one additional mol. of 2- 
amino ANTHRAQUINONE in naphthalene or other neutral solvent of high b.p. Red to brown 
powds., sol. in conc. sulf. (OR-Br); YELLOW to BROWN to red BROWN vat (RBr) dyes. 

S. 836—“‘Helindon Brown 3 GN.” Note that formula in Schulz is incorrect, the second 
part of reaction being omitted. 
958,850—May 24, 1910. Wilhelm BrERcHELMANN, Germany. (Bayer.) 
Wool dye. Sulfo acids of alfa amino anthraquinones, combined with epichlorhydrin. 

1.4-Diamino ANTHRAQUINONE or other alfa amino deriv., warmed at 30-35° with £EPI- 
CHLORHYDRIN in glac. acetic soln., separated and sulfonated in 1o parts fuming acid (five 
per cent SO,) at 15-20°. Dark powds., sol. in aq. (R-B), in conc. sulf. (R-VR); RED, BLUE, 
to VIOLET acid dyes. 


960,182—May 31, 1910. Walter Mirec, Germany. (Bayer.) 
Gray anthraquinone dye. Amino 1.1’-dianthrimids. 

1-Amino ANTHRAQUINONE, the diamino deriv. or other alfa amino deriv., and 1-2 mols. 
1-chlor ANTHRAQUINONE condensed to form 1.1/-DIANTHRIMID, then nitrated and reduced. 
Dark powds., not sol. in usual organic solvents, diff. sol. in quinolin, sol. in conc. sulf. (G) 
turning with HCHO to (V); Gray vat (GBr) dyes. 

S. 834—“‘Algol Gray B.” 
961,047—June 7, 1910. Fritz ULLMANN, Germany. (Berlin.) 
Anthraquinone acridones. Anthraquinone 1.2-acridone. 

1-Nitro ANTHRAQUINONE, or alfa chlor deriv., and ANTHRANILIC acid combined to form 
1-anilino ANTHRAQUINONE 2/-carbo acid or other, then condensed with PCI, and AICl, in 
benzene soln. Products are insol. in alc. and ether, easily sol. boiling anilin (V), in conc. 
sulf. (R); RED to VIOLET vat dyes. 

Note 961,048. 
961,048—June 7, 1910. Fritz ULLMANN, Germany. (Berlin.) 
Anthraquinone-diacridones. Anthraquinone 1.2-5.6-diacridone. 

1.5-Dichlor ANTHRAQUINONE and ANTHRANILIC acid condensed to form 1.5-dianilino AN- 
THRAQUINONE 2/.2”-dicarboxylic acid or other, which is condensed with PCI; and AICI, by 
warming at 1oo° until HCl ceases to evolve. Dark blue powd., sol. in conc. sulf. (O-Y), insol. 
alc. and ether, sol. in hot aniline (V); blue vioLter vat (B) dye. 

S. 832—‘“Indanthrene Violet RN.” Schulz credits this dye to the Badische Co. Addition to 


961,047. 


GROUP III.—ANTHRAQUINONE AT 


961,612—June 14, 1910. Max H. Ister and Hugo Wotrr, Germany. (Badische.) 


Anthracene compound and process of making it. Dihalogen dianthraquinonyl di- 
amino anthraquinone. 


1-Amino 6- or 7-chlor ANTHRAQUINONE or other amino chlor deriv. in which the chlorine and 
amino group are attached to different rings of the anthraquinone rest is boiled in nitrobenzene 
with Na,CO, and CuO. Lists of components claimed are given. Products are insol. in aq., alk., 
acids, diff. sol. in organic solvents, sol. in conc. sulf. (G) on warming bluer, containing more 
than nine per cent halogen; rED vat (YR-BrR) dyes. 

S. 827—“Indanthrene Bordeaux B.”’ Addition to 863,397. 


968,533—Aug. 30, 1910. Heinrich Bronratowsx1, Switzerland. (Basle.) 
Gray vat dyes and process of making. Halogen dinaphthanthraquinonyl imin. 

Amino NAPHTHANTHRAQUINONE (from 1-chlor NAPHTHALENE, PHTHALIC anhydride and NH,) 
condensed in nitrobenzene soln. by SbCi; and then halogenated at 60-100° in 20 parts conc. sulf. 
by passing in vapor of halogen. Black powds. sol. in hot C,H;NO, (VB-B), in conc. sulf. (Br); 
a blue Gray vat (B) dye, fast to washing, light Cl. 


970,278—Sept. 13, 1910. 
Paul THomascHEwsk1, H. Rareper, W. Mike, and P. Fiscurr, Germany. (Bayer.) 
Anthracene vat dye. Benzoyl amino di or tri anthraquinonyl amins. 

Benzoyl 1.4-diamino ANTHRAQUINONE, condensed with 1 mol. 2-chlor ANTHRAQUINONE, or other 
(see lists), in nitrobenzene soln. containing CuClz2 and sod. acetate. Colored powds., sol. in 
pyridone and quinolin (R-Br-G), in conc. sulf. (RBr-B-G); RED, VIOLET, BROWN, GREEN Of GRAY 
vat dyes. 


970,878—Sept. 20, 1910. Rene Boun, Germany. (Badische.) 
Vat dye and process of making same. Possibly a di-indanthrene. 

INDANTHRENE BLUE, or sulfo acid, heated at 100° in ninety-four per cent sulfuric with boric 
acid,—apparently a method for condensation, the sulfo group being eliminated, according to patent. 
Product is insol. in aq., alc., acids, alks., somewhat sol. in glac. acetic and C,H,Cl, (B), easily 
sol. in C,H,NO, (GB); green BLUE vat dye, greener than original indanthrene. 

S. 840—“‘Indanthrene Blue 3 G.’”’ Addition to 948,204. 


971,224—Sept. 27, 1910. 
P. THomMascHEWSKI, H. RaEpER, W. Mtec, and P. Fiscuer, Germany. (Bayer.) 
Bluish-gray wat dye. Dibenzoyl 4.4’-diamino dianthraquinonyl amin. 

Benzoyl 1-amino 4-chlor ANTHRAQUINONE, condensed with one mol. benzoyl 1-amino 4-amino 
ANTHRAQUINONE, by boiling in nitrobenzene containing anhyd. sod. acetate and CuCl, A dark 
powd., of metallic luster, sol. in conc. sulf. (G-Br); a blue Gray vat dye. 

Note 971,225. 


971,225—Sept. 27, 1910. (Re. 13,257—June 13, 1911.) 
P. THomascHEwsk1, H. Rageper, W. Miesc, and P. Fiscusr, Germany. (Bayer.) 
Brown wat dye. Dibenzoyl 4.5’-diamino dianthraquinonyl amin, sulfo acid. 
Benzoyl 1-amino 4-amino ANTHRAQUINONE, condensed with benzoyl 1-amino 5-chlor ANTHRA- 
QUINONE by boiling 3 hours in nitrobenzene containing anhyd sod. acetate and CuCO,. Melt 
is pptd. by toluene, separated and heated at 60—S0° in 10 parts conc. sulf. acid. A brown black 


powd., sol. conc. sulf. (Br); Brown vat dye. 
Near S. 833—‘‘Algol Olive R,” by another process. Addition to 971,224. 


975,863—Nov. 15, 1910. Eduard Herp and Christoph Hartmann, Germany. (Hochst.) 
Anthraquinone derivatives and process of making same. Composition not stated. 


1.5-Amino ANTHRANOL, heated with or without a solvent such as nitrobenzene or dil. HCl, 
and with or without condensing or oxidizing agent, passing air in for 24 hours when oxidizing 
agent is not present. Dark powds., insol. in aq., alk., acids, diff. sol. in organic solvents, sol. in 
pyridin and C,H,;NO, (BV); Gray to BLACK vat dyes, fast to light and alks. 


985,352—Feb. 28, 1911. Max KuceE., Germany. (Bayer.) 
Anthraquinone vat dye. N-Methyl indanthrene and homologs. 


1-Amino 2-brom ANTHRAQUINONE and methyl 1-amino 2-brom ANTHRAQUINONE or other 1- 
amino or alkyl amino deriv. with halogen in ortho position, boiled in naphthalene containing 


42 DIGEST OF PATENTS 


anhyd. CuSO, and sod. acetate. Method of dyeing is given. Blue powds., sol. boiling C,H,NO, 
(BG), in cone. sulf. (YBr-G); BLUE to green BLUE vat dyes. 
Addition to 775,367-68-69. 


986,521—Mar. 14, Iog11. 
Paul THomascHEwskI and Heinrich RaEpER, Walter Mrxrc, and Paul Fiscurer, Germany. (Bayer.) 
Yellowish-red wat dye. Benzoyl 5-amino 2.1’-dianthraquinonyl amin. 

Benzoyl 1-amino 6-chlor ANTHRAQUINONE and I-amino ANTHRAQUINONE condensed by boiling 
in naphthalene with CuCl, and anhyd. sod. acetate. A brown powd., sol. in pyridin and 
C,H,NO, (BrO), in conc. sulf. (B); an orange RED vat (B) dye. 


989,602—Apr. 18, 1911. Franz Henize, Germany. (Hochst.) 
Manufacture of amino-aryl-acidyl-amino-anthraquinones and their acidyl 

derivatives. Benzoyl 4’-amino benzoyl 1-amino anthraquinone and other aryl acidyl de- 

rivatives. 

4’-Nitro benzoyl 1-amino ANTHRAQUINONE or other (from amino anthraquinone condensed 
with nitro aryl acid chloride), reduced to amino compound which may be combined with 
BENZOYL chloride, or other aryl acidyl comp. (See tables). Yellow to red-brown powds., insol. 
in aq., alks., acids, sol. only in organic solvents of high b. p., such as C,H;NO,; YELLOW, RED 
to BROWN vat (R-Bk) dyes. 


992,567—May 16, 1911. Max A. Kunz, Germany. (Badische.) 
Anthracene dye. 3.3’-Dimethyl indanthrene or isomers, homologs, etc., containing at deeat 

one methyl group attached to an anthracene residue. 

2-Amino 3-methyl ANTHRAQUINONE, isomer or homolog, boiled in glacial acetic with PbO, or 
other condensing agent to form 3.3/-dimethyl INDANTHRENE or isomers. For (7.7’) product, 
boil in alkali. Products are insol. in aq., alk., and acids, more sol. in C,H;NO, than non- 
methylated indanthrene blue; BLUE to GREEN vat dyes. 

Note 682,523, 739,145 and 855,248. 


993,735—May 30, 1911. Paul THoMASCHEWSKI, Germany. (Bayer.) 
Vat dye. Dibenzoyl 4”.4”’-diamino dianthraquinonyl 4.4’-diamino diphenyl sulfone. 


4.4’-Dichlor DIPHENYL sulfone, condensed with two mols. benzoyl 1-amino 4-amino AN- 
THRAQUINONE by boiling in naphthalene soln. with CuCl, and anhyd. sod. acetate. Other di- 
halogen diaryl sulfones and amino anthraquinones are clees: Dark powds., sol. in quinolin 
{OR-B), in conc. sulf. (G); RED, VIOLET, BLUE tO GREEN vat dyes, fast to boiling, light and Cl. 
Note 993,736. 


993,736—May 30, 10911. Paul THOoMASCHEWSKI, Germany. (Bayer.) 
Vat dye. 1.1’-Dianthraquinonyl benzidin and derivs. 


4.4'-Dichlor DIPHENYL or other poly halogen diaryl comps., condensed with two mols. 1- 
AMINO ANTHRAQUINONE or at least 2 mols. of any other amino anthraquinone. Dark powds., sol. 
in pyridin (BR-B-V), in conc. sulf. (Y-Br-BrG); RED, VIOLET, BLUE to GREEN vat dyes. 

Addition to 993,735. 


993,992—May 30, I9g11. Wilhelm HeErzperc and Walter Brucx, Germany. (Berlin.) 
Vat dye of the anthraquinone series. Phenyl 1-anthraquinone thiazol, homologs and 
derivs. 


2-AMINO ANTHRAQUINONE or other beta amino deriv., condensed with BENZALDEHYDE to form 
benzylidin 2-amino ANTHRAQUINONE, which is heated at 220-230° with sulfur. Yellow to brown 
powds., diff. sol. in organic solvents (Y-Br), sol. in cone. sulf. (GY-Br), pptd. on diln. (Y); 
YELLOW, ORANGE to BROWN vat dyes. 


994,756—June 13, 1911. . Max Kucrr, Germany. (Bayer.) 
Vat dye. 3.3’-Dibrom N-methyl indanthrene. 


2-Amino 1.3-dibrom ANTHRAQUINONE, condensed with methyl 2-amino 1.3-dibrom ANTHRA- 
QUINONE by boiling in naphthalene containing anhyd. sod. acetate, Ca(OH),, and Cu,Cl,. Method 
of dyeing from cold vat is given. Dark blue cryst., diff. sol. in C,H;NO, (B), in conc. sulf. (Br); 
BLUE vat dyes. 


GROUP III.—ANTHRAQUINONE 43 


994,803—June 13, 1911 Oskar Uncrr and Paul THomascuEewsxk1, Germany. (Bayer.) 
Dye. Disulfo phenyl amino N-methyl anthrapyridone, and derivs. 


Phenyl 4-amino N-methyl anrHRAPYRIDONE (from brom compound and anilin) or derivs., 
sulfonated to disulfo or polysulfo acid in phenyl radicle. Alk. salts are dark red powds., sol. in 
aq. and alc. (R), in conc. sulf. (R), with boric acid (GY to O-fluor); RED acid dyes. 

Note addition 853,041 and 995,306 for specific patent. 


995,306—June 13, 1911. Oskar Uncrr and Paul THomascHEWSKI, Germany. (Bayer.) 


4-Metachlorophenylamino-1l-anthra-N-methylpyridon.. Disulfo 3’-chlor phenyl 4- 
amino N-methyl anthrapyridon. 


3’-Chlor phenyl 4-amino N-methyl aNtTHRAPYRIDON (from brom compound and meta chlor 
anilin) sulfonated to disulfo acid in phenyl residue. Dark red powd., sol. conc. sulf. (VR), with 
boric acid (YR with O fluor); yellow rep acid dye. 

Note 994,803 for general claims. 


995,936—June 30, 1911. Hugo Wo.LFr, Germany. (Badische.) 


Green anthracene dyes and process of making the same. Benzanthronyl 1-amino 
anthraquinone condensed in alkali. 


BENZANTHRONE treated in aq. suspension with Cl to form the mono chlor deriv. which is 
condensed with 1-amino ANTHRAQUINONE and product heated in KOH at 240-245°. Alcohol may 
be present and metallic Na in abs. alcohol used in place of fused KOH. Green black powds., insol. 
in aq., sol. in C,H;NO,, quinolin and conc. sulf. (G); GREEN vat (BV) dye. 


996,109—June 27, 1911. Walter Mirc, Germany. (Bayer.) 


Olive-gray vat dye. Dibenzoyl 4.4’-diamino dianthraquinonyl amin with oxygen removed 
from carbonyl of anthraquinone and residual carbon linking the amino nitrogen and 2 position 
in the other anthraquinone rest. 


Dibenzoyl 4.4’-diamino 1.1/-DIANTHRIMIN, produced from benzoyl 4-amino 1-chlor ANTHRA- 
QUINONE condensed with benzoyl 1.4-diamino ANTHRAQUINONE, heated in 66° sulf. acid till brown, 
then more fuming acid added. Dark powds., sol. in conc. sulf. (R); olive Gray vat dye. 

Addition to 971,224. 


996,487—June 27, 1911. Michael Injinsxy, Germany. (Wedekind.) 


Process of making acid dyes of the anthracene series. 1.5-Dianilino 2.6-dioxy 3.7- 
disulfo anthraquinone and derivs. 


Dinitro disulfo ANTHRAFLAVIC acid (made by sulfonating ANTHRAFLAVIC acid with or without 
boric, then nitrating) heated with ANILIN or other aromatic amin with or without ANILIN HCl or 
Na,S and S at 140-145°. The alkali soluble portion of product which is separated is valuable 
as a dye; BROWN, brown RED, violet RED, BLUE and blue GREEN acid or acid mordant (Cr) dyes. 

S. 857—“Erweco Alizarin Acid Blue R.” 


998,156—July 18, 1911. Max Burr, Germany. (Bayer.) 
Blue vat dye. N-hydrogen in isatin substituted by 4-alphyl amino 1-anthraquinone. 
Methyl 4-amino 1-brom ANTHRAQUINONE or other alphyl amino deriv., condensed with ISATIN 


by boiling in nitrobenzene containing sod. acetate and Cu,Cl,. Dark powds., diff. sol. in most 
organic solvents, sol. in conc. sulf. (Br); BLUE vat (Br) dyes. 


998,772—July 25, 1911. Max HerssENLAND, Germany. (Hochst.) 
Blue dye-stuff and process of making same. 4-Amino anthraquinone a-acridone. 
4-Amino 1-anthraquinonyl ANTHRANILIC acid, dissolved in chlor sulfonic acid at 10-20°. A 


green blue powd., insol. in aq., alc., ether, slightly sol. in glac acetic, sol. in C,H,NO, and 
recryst therefrom, sol. in conc. sulf. (Br); green BLUE vat (V) dye. 


999,6S80—Aug. 1, I9gII. Friedrich S1ncER, Germany. (Griesheim.) 


Vat dyestuff of the anthracene series. (Process also claimed.) Two or more mols. 
dianthrene condensed, or other similar derivs. 


DIANTHRONE, (obtained by oxidization of ANTHRANOL with FeCl, in glac. acetic soln.), heated 
at 120-160° with AICI, or other condensing agent in nitrobenzene soln. Other products of re- 
duction of anthraquinone, such as bianthrone and dianthranol are also claimed. Brown black 
powds., sol. conc. sulf. and in conc. HNO, (BrV) then decomp., in warm Na,S (VBr); fast 
BROWN vat (RBr) dyes. : 

4 


44 DIGEST OF PATENTS 


999,785—Aug. 8, tort. Max HEssENLAND, Germany. (Ho6chst.) 
Vat dyestuff. Anthraquinonyl 5’-amino anthraquinone 1.2-phen-thioxanthone. 


1-Chlor 5-amino ANTHRAQUINONE (or dichlor compound), condensed with thio saLicyiic acid 
and chlor sulfonic acid to form 5-amino anthroquinone 1.2-phen-THIOXANTHONE, which is refluxed 
with 1-chlor ANTHRAQUINONE or amino comp. in nitrobenzene soln. with CuCl, and sod. acetate. 
Red to gray blue powds., diff. sol. usual solvents; sol. in conc. sulf.; violet RED vat (BrV) dyes. 
Note 1,007,104. 


999,798—Aug. 8, 1911. Georg. KatiscHEr, Germany. (Cassella.) 


Vat dye and process of making same. Probably internal condensation of components 
forming new inside nucleus aggregates or indanthrenes. 


1/.1”-Dianthraquinonyl 1.5-diamino ANTHRAQUINONE obtained from 1.5-diamino ANTHRAQUI- 
NONE and two mols. 1-chlor ANTHRAQUINONE, heated with anhyd. AICl, at 220-240°. Other com- 
ponents claimed. Dark powds., insol. in aq., slightly sol. organic solvents, sol. in conc. sulf. 
(V-B); brown ORANGE to BROWN vat (Y-R) dyes, fast to washing, light, Cl. 

Addition to 863,397. 


1,001,325—Aug. 22, IgIt. Fritz ULLMANN, Germany. (Berlin.) 


Product of the anthraquinone series and process of making same. (Process 
not claimed.) N-Phenyl anthraquinone pyrazolone derivs. and other nonmetallic N-sub- 
stituents. 


ANTHRAQUINONE 1-Carbo acid or other alfa carbo acid refluxed in glac. acetic acid with 
PHENYL hydrazin or a deriv. thereof. Yellow powds., diff. sol. alc., and ether, sol. in conc. 
sulf. (Y-O with fluor) that may serve as intermediates or as dyestuffs; yELLow vat dyes. 


1,001,408—Aug. 22, 1911. Max H. Isier, Germany. (Badische.) 
Anthracene compounds and making same. Mono or di-phenanthridone anthraquinone, 
or derivs. 


Benzoyl 1-amino 2-brom ANTHRAQUINONE or other 1-benzoyl amino ortho halogen derivs., con- 
densed to phenanthridone ANTHRAQUINONE by boiling in naphthalene soln. in presence of calcined 
Na,CO, or anhyd. sol. acetate, with or without Cu powd. Yellow powds., sol. in conc. sulf., 
diff. sol. in ordinary solvents; YELLOW vat dyes. 


1,002,066—Aug. 29, 1911. Arthur Lutrrincuaus, Germany. (Badische.) 
Vat dye. 4’-Chlor 1.2-anthraquinone acridone. 


1-Chlor ANTHRAQUINONE 2-carbo acid, condensed with 4-chlor ANILIN by heating 2-3 hours at 
160° in dimethyl anilin containing Cu powd., separated, and further condensed at 90-100? in 
conc. sulfuric acid. A yellow red powd., sol. hot amyl acetate (R), insol. in sixty-five per cent 
H,SO,, sol. in seventy per cent sulf. (OY); violet RED vat dye. 

Note 1,002,270. 


1,002,270—Sept. 5, 1911. Max HeEssENLAND, Germany. (Héchst.) 


Vat dyestuff of the anthraquinone series and process of making same. An- 
thraquinonyl 4-amino 1.2-anthraquinone acridone. 


4-Amino ANTHRAQUINONE 1.2-acridone (from 4’-amino anthraquinonyl anthranilic acid and 
chlor sulfonic acid) condensed with 1-chlor ANTHRAQUINONE, or halogen alkyl, aryl, acidyl, or 
other anthraquinone deriv. Table of reactions of comps. given. Dark powds., insol. in aq,, alc., 
ether, acids, alks., sol. in conc. sulf. (G-Br); Gray to BLACK vat (V-BR): dyes. 

Addition to 1,002,066. 


1,003,268—Sept. 12, 1911. Richard Just and Hugo Wotrr, Germany. (Badische.) 
Anthracene dye and process of making same. Dibrom iso violanthrone or other 
halogen deriv. 

Halogen BENZANTHRONE treated with caustic to form iso VIOLANTHRENE, heated gently at 50— 
60° with SO,Cl, or other chlorinating agent in nitrobenzene soln. to form dichlor or dibrom 
compound. Dark blue to violet powds., insol. in aq., alks., acids, sol. in conc. sulf. (G), in 
C,H;NO, (R); red to blue vioter vat (B) dyes. 

S. 767 and 768—“Indanthrene Violet 2 R and B.” Note 837,775 and 906,367. 


1,004,107—Sept. 26, 1911. Paul TuHomascHEwsk1, Germany. (Bayer.) 


Violet wool-dye. Tolyl amino anthraquinone in which oxygen of one carbonyl and ortho H, 
(para to NH,) are substituted by alkyl urea. 


GROUP III.—ANTHRAQUINONE 45 


Methyl 1-amino 4’-tolyl 4-amino ANTHRAQUINONE and equal weights of urEA and NH,Cl 
boiled in phenol soln., pptd. by alcohol, separated and heated at 50° in 10 parts conc. sulfuric 
acid to which fuming acid is added until mixture fumes. Alkaline salts are violet powds., sol. in 
aq. (V); vioLeT acid dyes when sulfonated. 


1,004,433—Sept. 26, 1911. Max F. Isnrer, Germany. (Badische.) 
Dianthraquinonyl-dialdehydes and process of making them. 1.1/-Dianthra- 
quinonyl 2.2’-dialdehyde, with CO and CHO groups condensed to form internal rings. 


1-Chlor ANTHRAQUINONE 2-aldehyde or derivs., condensed in naphthalene soln., containing 
alk., carbonate and copper, to 1.1’-DIANTHRAQUINONYL 2.2/-dialdehyde which can be reduced and 
further condensed in hydresulfite vat and at the same time dyed on cotton. Other components 
claimed. Products are insol. in NaOH, sol. in conc. sulf. (R), diff. sol. most organic solvents 
except high b. p. solvents when hot; treated with condensing agent in vat give RED to YELLOW 
vat (R) dyes. 

Note 856,911 for similar comps. produced from the 2.2’-alkyl derivs. 


1,007,104—Oct. 31, 1911. ; Max HEssENLAND, Germany. (Hochst.) 


Vat dyestuffs of the anthraquinone series and process of making same. 4- 
Amino anthraquinone 1.2-thioxanthone. 


4-Amino ANTHRAQUINONE 1-thio salicylic acid or derivs. (from 1-chlor 4-amino ANTHRA- 
QUINONE and thio sanicyLic acid) condensed at 15—-20° with chlorsulfonic acid, or other de- 
hydrating agent. Blue powds., insol. in aq., alc., ether; BLUE vat (VB) dyes. 

Addition to 999,785. 


1,008,906—Nov. 14, 1911. Wilhelm Hrrzsrrc and Walter Bruck, Germany. (Berlin.) 
Vat dyes of the anthraquinone series. Mono or dihalogen phenyl anthraquinone 1.2- 
acridone. 


ANTHRAQUINONE 1.2-acridone or deriv. (from 1-chlor ANTHRAQUINONE and ANTHRANILIC 
acid), mono or di-brominated in benzene nucleus, in nitrobenzene soln., or in sulf. acid at 0°. 
Products are insol. in alc. or C,H,, diff. sol. in C,H;NO,, sol. conc. sulf. (Y); RED to BLUE vat 
dyes. 

Note 1,008,908. 


1,008,908—Nov. 14, 1911. Wilhelm Hrrzperc and Walter Brucx, Germany. (Berlin.) 
Vat dyes of the anthraquinone series. Benzoyl amino phenyl 1.2-anthraquinone acri- 
done or other acidyl derivs. 

ANTHRAQUINONE acridone or deriv., nitrated and reduced to amino compound then condensed 
with BENZOYL CHLORIDE, or other acidyl amino comp., or an anthraquinone halogen acridone and 
an amid of an organic acid are combined. Products are blue powds., insol. in usual solvents, 
diff. sol. C,H;NO,, sol. conc. sulf. (OR); BLUE vat dyes. 

Addition to 1,008,906. 


1,009,981—Nov. 28, 1911. Rudolf Lesser, Germany. (Héchst.) 
Process of dyeing with benzoquinone derivatives. Quinone diarylids, homologs 
and halogen derivs., applied as vat dyes. 

QuinoneE dianilid or other benzoquinone derivs., in dil. NaOH soln., reduced with hydro- 
sulfite to form vat in usual manner. YELLOW, RED to BROWN reducing vat dyes, developed by air 
or oxidizing agent. ; 

Note that some of these products are already known but not as dyes. 


1,010,463—Dec. 5, 1911. Paul THomascHEwsk1, Germany. (Bayer.) 


Vat dye. Di anthraquinone 1.2 sulfoxid and deriv. 


ANTHRAQUINONE 1-mercaptan, three parts, or other anthraquinone mercaptan, and four parts 
I-OXy ANTHRAQUINONE or other oxy anthraquinone, heated in ninety-eight per cent sulfuric at 
160-170°. Products may be recryst. from boiling quinolin, as red brown needles sol. in boiling 
naphthalene (O), in conc. sulf. (G); ORANGE RED vat dyes. 


1,010,930—Dec. 5, tort. Arthur Lurrrincuaus, Germany. (Badische.) 


Vat dye. 3.4-Dichlor phenyl anthraquinone acridone with chlorine in benzene ring, in meta 
and para positions to NH. 


1-Chlor ANTHRAQUINONE 2-carbo acid or derivs., condensed with 3.4-dichlor aninin. A red 
powd., sol. in hot anilin (VR), insol. in seventy per cent sulf., containing Cl; a rEp vat dye. 


46 DIGEST OF PATENTS 


1,011.068—Dec. 5, 1911. Arthur Lurrrincuaus, Germany. (Badische.) 
Vat dye. Anthraquinone 1.2-naphthacridone. 


1-Chlor ANTHRAQUINONE 2-carbo acid boiled in aq. soln. containing copper powd. and car- 
bonates, with 2-NAPHTHYLAMIN, the resulting 2-naphthylamin ANTHRAQUINONE carbo acid sepa- 
rated and heated with 1.2-dichlor BENZENE and PCI, or other condensing agent. A red powd., 
diff. sol. boiling C,H;NH, (BrR), sol. seventy per cent sulf. (OY), pptd. on standing, insol. 
sixty-five per cent sulf.; a RED vat dye. 

S. 831—“‘Indanthrene Red BN.” 


1,014,204—Jan. 9, 1912. Wilhelm BercHELMANN, Germany. (Bayer.) 
Dye. Sulfo acids of dihydroxy diethyl 1.4-diamino anthraquinone or derivs. 


1.4-Diamino ANTHRAQUINONE, the mono amin or other deriv., condensed in nitrobenzene 
soln. with two mols. ETHYLENE oxide, glycid, propylene oxid, etc., then sulfonated, or sulfo 
derivs. of components may be used. Dark powds., sol. in aq. (R-B), in conc. sulf. (R-VR); 
RED, BLUE tO VIOLET acid dyes, fast to light. 


1,015,329—Jan. 23, 1912. Rudolf Maac, Germany. (Hoéchst.) 
Vat dyestuffs and process of making same. Benzoquinone 4’.4”-dibrom dianilid. 


BENZOQUINONE condensed with ANILIN to dianilid then brominated in nitrobenzene soln. at 
170-200° to dibrom product, with bromin in para position to NH groups of anilin rest. Yellow 
brown to red brown powds., insol. in alc., ether, C,H,, sol. in C,H,;NO, (BrR), in conc. sulf. 
(V); fast YELLOW vat (Yt) dyes. 

Note 1,018,433 and 1,025,147. 


1,016,604—Feb. 6, 1912. Oscar Batuy, Germany. (Badische.) 


Anthracene dye and process of making same. 1’.1”-Dianthraquinonyl 4.4’-diamino 
benzophenone or other. 


4.4’-Dichlor BENZOPHENONE mono brom phenanthrone quinone, or other halogenated ketone, 
condensed with two mols. 1-amino ANTHRAQUINONE or other amino deriv. by heating in nitro- 
benzene with CuCl, and anhyd. sod. acetate. See table of reactions. Dark powds., sol. conc. 
sulf. (V-Br-G), in fuming sulf. (G-B), sol. C,H,NO, (Br-R); RED to vioLET vat dyes. 

Addition to 863,397. 


1,016,638—Feb. 6, 1912. August L. Lasxa, Germany. (Griesheim.) 
Vat dye and process of making same. 2’-Anthraquinonyl 1.2-azimino naphthalene, or 
derivs. 


2-Amino ANTHRAQUINONE, 2.6-diamino or other beta amino deriv., diazotized in conc. H,SO,, 
coupled with 2-NAPHTHYLAMIN or other beta aryl amino deriy., separated and oxidized with 
chromate. Product is sol. in conc. sulf. (BrO-RBr), pptd. on diln. (Y); yELLow vat (BrV) dyes, 
fast to’: washing and Cl. 


1,018,433—Feb. 27, 1912. Rudolf Maac, Germany, (Héchst.) 


Brown wat dyestuff and process of making same. Halogen benzoquinone di-naph- 
thalid with halogen in benzene nucleus. 


1-NAPHTHYLAMIN, or other aryl amin, boiled in alc. containing NaC,H,O,, with CHLORANIL, 
tetra chlor benzoquinone or similar comp. Brown powds. insol. in aq., alc., C,H,, sol. in conc. 
sulf. (B); fast BRowN vat dyes. J 

Addition to 1,015,329. Note 1,025,147. 


1,018,836—Feb. 27, 1912. 
Arthur Lurrrincuaus and Heinrich von Dirspacnu, Germany. (Badische.) 
Orange-red vat dye. Anthraquinone 4-methyl 1.2-thioxanthone. 


1-Chlor ANTHRAQUINONE 2-carbo acid, combined with 4-thio crEsot and condensed to thio 
xanthone in trichlor benzene soln. with PCI,. Red powd., sol. in conc. sulf. (R); an orange 
RED vat (V) dye, fast to Cl and light. 

Note 1,018,837. 


1,018,837—Feb. 27, 1912. 
Arthur LutrrincuHaus and H. von Drigespacu, Germany. (Badische.) 
Yellow vat dye. Dianthraquinone 1.2-thioxanthone, and derivs. 


1-Chlor ANTHRAQUINONE 2-carbo acid combined with 2-mercapto ANTHRAQUINONE by reflux- 


GROUP III.—ANTHRAQUINONE 47 


ing in dil. KOH, separated and condensed to xanthone at 100° in 1o parts conc. sulfuric acid. 
Yellow to brown yellow powds., sol in conc. sulf. (RBr); yELLow vat (GB-BBk) dyes. 
Addition to 1,018,836. 


1,022,781—Apr. 9, 1912. Hermann FrigpMAnN, Germany. (Bayer.) 
Vat dye. Benzoyl 4-amino phenyl 1.2-anthrimidazol and derivs. 


1.2.4-Triamino ANTHRAQUINONE condensed in nitrobenzene soln. with BENZALDEHYDE or other 
aromatic aldehyde, to form 4-amino phenyl 1.2-ANTHRIMIDAZOLE which is condensed with 
BENZOYL chloride. Dark powds., which before being acidylized are BLUE to GREEN vat dyes 
and after acidylation are ORANGE vat dyes, fast to light. 

Note 1,023,248. 


1,023,248—Apr. 16, 1912.. Hermann FriepMANN, Germany. (Bayer.) 
Vat dye. Benzoyl 4-amino 2’-chlor phenyl 1.2-anthrimidazol. 


1.2.4-Triamino ANTHRAQUINONE condensed in nitrobenzene soln. with 2-chlor BENZALDEHYDE or 
other aryl deriv., and with pENzoyL chloride, by heating to 150°. Yellow to orange powds., sol. 
in conc. sulf. (R); YELLOW to red ORANGE vat (R-Br) dyes, fast to light, washing and ironing. 
Addition to 1,022,781. 


1,023,847—Apr. 23, 1912. Max HeEssENLAND, Germany. (Hochst.) 


Alizarin-red vat dyestuff and process of making same. 2/-Chlor 1.2-anthraqui- 
none acridone and derivs. 


s’-Chlor 2’-carbo phenyl 1-anilino 1-ANTHRAQUINONE, from 4-chlor 2-amino BENzorIc acid and 
1-chlor ANTHRAQUINONE, condensed with chlor sulfonic acid or other dehydrating agent to close 
acridone ring. Yellow red powds., insol. in usual organic solvents but recryst. from C,H,NO,., 
sol. conc. sulf. (Br); RED vat dyes. 


1,025,147—May 7, 1912. Rudolf Maac, Germany. (Hoéchst.) 
Vat dyestuff and process of making same. 2.6-Dichor benzoquinone 4’.4”-dichlor 
dianilid. 


4-Chlor ANILIN 2 mols., or homologs, condensed with 2.6-dichlor BENZOQUINONE or deriv., by 
boiling in 16 parts alcohol. Yellow brown to brown red powds., insol. in alc., ether and 
C,H,, sol. in hot glac. acetic and C,H;NO, (BrR), in conc. sulf. (V); fast yELLOw vat (Yt) dyes. 
Note 1,015,329 and 1,018,423. ; 


1,025,195—May 7, 1912. Georg KranzLEIn, Germany. (Hd6ochst.) 
Salmon-colored wat dyestufi and process of making same. Possibly 2.2’-dianthra- 

quinonyl ureas. 

2-ANTHRAQUINONYL urea chloride, condensed from 2-amino ANTHRAQUINONE and PHOSGENE 
other formic acid deriv., boiled in nitrobenzene soln. with anhyd. sod. acetate or other alk. con- 
densing agent. Red brown powd., insol. in ag. and usual solvents, sol. in conc. sulf. (YG-BG), 
upon heating (B); pale red orancE vat (OBr) dyes, fast to washing, light, Cl. 

S. 835—‘‘Helindon Orange GRN.”’ 


1,026,557—May 14, 1912. Johann H. Boner and Oscar Batuy, Germany. (Badische.) 
Anthracene compounds and process of making same. 1,.4-Ditoluidino 2-sulfo an- 
thraquinone or derivs. 


ANTHRAQUINONE 2-sulfo acid or deriv., halogenated at 160° in ninety-six per cent sulfuric 
or fuming acid to 1.4-dichlor product, using iodine or its chloride as carrier, separated and 
heated at 150° in an autoclave with ammonia or 4-TOLUIDIN, or other amin, then sulfonated or 
not. Products are sol. in aq. (R-BG), in conc. sulf. (GBr-B); rep to blue GREEN acid dyes. 


1,026,588—May 14, 1912. Max H. Isxer, Germany. (Badische.) 
Anthracene dyes and process of making same. 2.2’/-Dianthraquinonyl thio ureas. 


2-Amino ANTHRAQUINONE 1.4-diamino or other deriv., boiled in nitrobenzene soln. with 1-2 
mols. trichlor METHYL sulfur chloride with or without catalyst (Cu) or agent to absorb HCl. 
Violet, red brown, or black powds., sol. in conc. sulf. (O-Br-B), in C,H,;NO, (V-Y-R-Br), 
hydroxy derivs. sol. in boiling NaOH (B); RED or VARI-COLORED vat dyes. 


1,026,621—May 14, 1912. Oscar Batty, Germany. (Badische.) 


Halogenated vat dyes and process of making same. Halogen anthraquinone 1.2.5.6- 
dithioxanthones, with at least one halogen in benzene nucleus. ; 


48 DIGEST OF PATENTS 


ANTHRAQUINONE 1.2.5.6-dithioxanthone, from halogen ANTHRAQUINONES and 2 mols. thio 
SALICYLIC acid, halogenated in nitrobenzene soln. Products are insol. in dil. acids, alks., sol. 
in conc. sulf. (Y-R); orange RED vat dyes or as sulfo derivs. YELLOW to RED acid dyes, of 
yellower shade than non-halogen comps. 


1,028,637—June 4, 1912. Paul THomascHEwsxk1, Germany. (Bayer.) 
Vat dye. Trianthraquinone dioxithin and derivs. 


ANTHRAQUINONE 1.5-dimercaptan or derivs., 1 mol., condensed with 2 mols. 1-oxy ANTHRA- 
QUINONE or derivs., or 2 mols. of the first with 1 mol. of the second, by heating at 160-170° in 
ninety-eight per cent sulfuric. Red to brown powds., sol. conc. sulf. (G-GB); RED to BROWN vat 
dyes. 

Note 1,010,463 for original application, also 1,032,215 and 16. 


1,032,215—July 9, 1912. Max IsterR, Germany. (Badische.) 
Anthraquinone dyes and process of making them. Dianthraquinone 1.2.1'.2/-di- 
sulfid and derivs. ; 


ANTHRAQUINONE 1.2-dimercaptan, condensed with 1.2-dichlor ANTHRAQUINONE or other alfa 
halogen deriv. by boiling in nitrobenzene soln. Red crysts., sol. in conc. sulf. (G-B); fast RED 
vat dyes. 

Addition to 1,028,637. 


1,032,216—July 9, 1912. Max Isuer, Germany. (Badische.) 
Anthraquinone wat dyes and process of making them, Dianthraquinone thiazin. 
2-Amino ANTHRAQUINONE 1I-mercaptan or deriv., condensed with 1.2-dichlor ANTHRAQUINONE 
or other halogen deriv., by boiling in nitrobenzene, naphthalene or other solvent. Violet blue 
crysts., sol. in conc. sulf. (G); fast vioLuT to BLUE vat (Y-Br) dyes. 
Addition to 1,028,637 and 1,032,215. 


1,034,895—Aug. 6, 1912. Herman FRIEDMANN, Germany. (Bayer.} 
Vat dye. a-Phenyl 4-amino 1.2-anthraquinone oxazole, or other aryl deriv. 

1-Oxy 2.4-diamino ANTHRAQUINONE, condensed in three parts nitrobenzene with one part 
BENZALDEHYDE or Other aldehyde. Products can be acylated to other dyes of same character. 


Brown powds., sol. in pyridin, in conc. sulf. (Y-Br); BROWN to ORANGE vat dyes. 
Note 1,034,896. 


1,034,896—Auzg. 6, 1912. Hermann Fri—EpDMANN, Germany. (Bayer.) 
Yellow wat dye. a-Phenyl benzoyl 4-amino 1.2-anthraquinone oxazole. 

1-Oxy 2.4-diamino ANTHRAQUINONE or derivs., condensed with BENZALDEHYDE or other alde- 
hyde to an oxazole which, is further condensed in same soln. with BENzoyL chloride or other 
acidyl chloride. Yellow to orange powds., sol. in sulf. (Y); YELLOW vat dyes, fast to light, wash- 
ing and ironing. 

Addition to 1,034,895. 
1,035,023—Aug. 6, 1912. Arthur LurtrincHaus and Wilhelm Brargen, Germany. (Badische.) 
Vat dyes and making the same. Formula not shown. 

3-Amino 4-methyl pIPHENYL ketone 2/-carbo acid, condensed with 1-chlor ANTHRAQUINONE 2- 
carbo acid to a dianthraquinone acridone in which CO of acridone ring is in gamma diketone 


position to CO of anthraquinone ring, then heated at 120° in cresol soln. with HypRAzIN hydrate, 
or sulfate. Dark crysts., insol. in organic solvents, in conc. sulf. (VR); fast Gray vat (Br) dye. 


1,036,880—Aug. 27, 1912. Carl MoLttENHOoFF, Germany. (Bayer.) 
Production of alizarin. Improved method of mfr. for alizarin. 

ANTHRAQUINONE 2-sulfo acid 2 parts heated at 180-200° in an autoclave in dilute NaOH of 
less than fifty per cent strength, with one part ANTHRAQUINONE, with or without oxidizing agent, 
such as 0.5 part NaNO.. 

S. 778—“‘Alizarin.” 


1,036,881—Aug. 27, 1912. Carl Motyenuorr, Germany. (Bayer.) 
Production of alizarin from anthraquinone. Improved mfr. of alizarin. 


ANTHRAQUINONE heated in autoclave at 180-200° in dil. NaOH (less than fifty per cent) con- 
taining alk. sulfite. 


S. 778—“Alizarin.” Note that previous methods have employed conc. alkali. 


GROUP III.—ANTHRAQUINONE AQ 


1,037,410—Sept. 3, 1912. Oscar Batty, Germany. (Badische.) 
Anthracene dye and process of making same. 1”.1”’-Dianthraquinonyl 4.4’-diamino 
diphenyl methane and derivs. 


4.4’-Dichlor DIPHENYL methane or other halogen dialphyl methane derivs., and 1-amino an- 
THRAQUINONE or deriv. refluxed in nitrobenzene containing CuO and calc. soda. Product may 
be sulfonated at 30° in fuming acid. Red brown powds., sol. in hot C,H,;NO, (R), in conc. sulf. 
(BrG), in fuming acid (G); a RED vat or in sulfonated form RED acid dye. 


1,038,003—Sept. 10, 1912. Albrecht Scumipt and Georg KranzLE1n, Germany. (Hochst.) 
Pure B-anthraquinonyl-urea-chlorid and process of making same.—z-Anthra- 


quinonyl urea chlorids free from 2-amino anthraquinone HCl. 


PuHOSGENE in excess of 1 mol. added to 1 mol. 2-amino ANTHRAQUINONE in nitrobenzene soln. 
at usual temp. or with gentle heat of from 4o-120°. Condensed with anilin or other amin product 
gives a YELLOW vat dye. 

S. 885—‘‘Helindon Orange GRN.” Patent claims only the intermediate, but is classed as 
dye by Schulz. Note D. P. 167,410. 


1,038,589—Sept. 17, 1912. Andreas Jacopi1, Germany. (Bayer.) 


Anthracene dye. 1.4-Diamino 2-phenoxy 3-chlor anthraquinone sulfo, or other beta aryloxy 
comp. with auxochrome group in para position. 
1.4-Diamino 2.3-dichlor ANTHRAQUINONE or other alfa amino beta chlor. deriv. boiled in 
phenol soln. with PHENOL, sod. salt, separated in dil. alk. soln. and sulfonated by gentle heating 
in 66° acid. Dark powds., sol. in aq.; RED Or VIOLET to BLUE vat dyes. 


1,042,931—Oct. 29, 1912. A. L.. Lasxa, A. ZitscHEeR and A. J. Ratu, Germany. (Griesheim.) 


Vat dyestuffs of the anthracene series and process of making same. [. An- 
thraquinonyl 1.2-azimino anthracene. IJ. Anthraquinyl 1.2-azimino anthraquinone. 
2-Amino ANTHRAQUINONE diazotized and coupled in acetic soln. with 2-amino ANTHRACENE, 

then heated at 100° in nitrobenzene with bichromate and glac. acetic to form a pseudoazimid or 

dye I., which can be further oxidized to dye II. Other complexes may contain three anthra- 
quinone nuclei. Products are sol. in conc. sulf. (Br), in hot C,H;NO, (Y); yELLow vat (Br) 
dyes. 


1,044,602—Nov. 19, 1912. Paul Thomaschewski, Germany. (Bayer.) 
Vat dyestuff. 1.1/.1”-Trianthraquincnyl dithio ether, and derivs. 

ANTHRAQUINONE 2-mercaptan, 2 mols. and 1 mol. 1.5-dichlor ANTHRAQUINONE boiled in 6 
parts naphthalene. Other similar components are claimed. Orange yellow powds., sol. in 
quinolin (OY) and cryst. therefrom in needles (OY), sol. cone. sulf. (GB); yELLow vat dyes, 
fast to Cl and light. 

Note 1,044,603. 


1,044,603—Nov. 109, 1012. Paul THOMASCHEWSKI, Germany. (Bayer.) 
Vat dyes. Benzoyl 4-amino 1.2/-dianthraquinonyl thio ether. 

ANTHRAQUINONE 2-mercaptan boiled with benzoyl 1-amino 4-chlor ANTHRAQUINONE in naph- 
thalene soln. containing alk. carbonate. Other components claimed. Red powds., sol. in conc. 
sulf. (Y-B-G); YELLOW, ORANGE to RED vat dyes, fast to Cl and light. 

Addition to 1,044,602. 


1,044,673—Nov. 19, 1912. 
Arthur Lutrrincuaus and H. von Dirsspacu, Germany. (Badische.) 
Orange-yellow vat dye. 4’.5’-Dichlor phen 1.2-anthraquinone thio xanthone. 


1-Chlor ANTHRAQUINONE 2-carbo, refluxed in dil. KOH soln. in absence of air, with 3.4- 
dichlor thio PHENOL to form thio ether which is heated at 100° in conc. sulf. until test with 
NaOH gives yellow color. Orange yellow powd., sol. in conc. sulf. (R); orange YELLOW vat (V) 
dye, fast to Cl and light. 

Note 1,044,674 and 75. 


1,044,674—Nov. 19, 1912. Arthur LuTrrincHAus and Ernst ScHwarz, Germany. (Badische.) 
Yellow vat dye. 3’6/-Dichlor phen 1.2-anthraquinone thio xanthone. 


1-Chlor ANTHRAQUINONE 2-carbo, refluxed in dil. caustic alkali with 2.4.5-trichlor thio PHENYL, 
thio PHENOL, separated, then condensed further to thioxanthone at 100° in io parts conc. sul- 


50 DIGEST OF PATENTS 


furic acid. Yellow powd., sol. in conc. sulf. (VR); xELLow vat (V) dye, fast to Cl, light, wash- 
ing. 
Addition to 1,044,673. 


1,044,675—Nov. 19, 1912. Arthur Lurrrincuaus and Ernst Scnwarz, Germany. (Badische.) 
Yellow wat dye. 3’.4’.6/-Trichlor phen 1.2-anthraquinone thioxanthone. 


1-Chlor ANTHRAQUINONE 2-carbo, refluxed in dil. caustic alkali with 2.4.5-trichlor thio PHENOL, 
then further condensed in conc. sulfuric acid at 100°. Yellow powd., sol. conc. sulf. (VR); 
YELLOW vat (V) dye, fast to Cl and light. 

Addition to 1,044,673. 


1,044,797—WNov. 19, 1912. Bertram Mayer and Leopold Wei, Switzerland. (Basle.) 


Process for the manufacture of a sulfureted wat dye of the anthracene 
series. Two mols. 2-methyl benzanthrone form two five membered rings with carbon of 
methyl groups, sulfur and nearest carbon of benzanthrone and two fesulting complexes 
unite by double linkage between methyl carbons. 
2-Methyl BENZANTHRONE m. p. 199° refluxed with 1 part sulfur in 5 parts naphthalene for . 

25 hours, filt. hot and solid washed with xylene. Blue GREEN vat dyes of clearer tints than 


when made without solvent. 
Addition to 927,868. 


1,044,933—Nov. 19, 1912. Fritz Sincer, Germany. (Griesheim.) 


Process of making vat dyes of the anthracene series. Probably indanthrenes of 

various kinds. . 

ANTHRAQUINONE or any deriv. of anthracene series containing intact keto groups and at 
least two substituents, heated to 250—300° with 0.75 weight AICl,. A table of properties is given. 
Black powds., insol. in aq., alks. and organic solvents, diff. sol. conc. sulf. (G); a BROWN vat 
(BkV) dye, or Gray sulfide vat (G) dye, fast to Cl. 

Addition to 655,248 and 739,145. 


1,045,805—Dec. 3, 1912. Wilhelm BercHELMANN, Germany. (Bayer.) 


Greenish-blue wool-dye. 5-Nitro 1.4-diamino anthraquinone with two amino groups con- 
“taining an epichlor-hydrin rest wherein the ring has been broken by a sulfo group. 
s-Nitro 1.4-diamino ANTHRAQUINONE warmed at 30-35° with FoRMIc acid and EPICHLOR- 
HYDRIN, product separated, purified and sulfonated in 20 parts fuming sulf. (five per cent SO,) [ 
at 10-15°. Alk. salt is blue powd., sol. in ag. (B), in conc. sulf. (Br-R); a green BLUE acid 
dye, fast to light. 


1,046,498—Dec. 10, 1912. Albrecht Scumipt and Georg KransLeIn, Germany. (Hochst.) 


Halogenized condensation product of the anthracene series and process of 
making same. Halogen anthranol quinone derivs. 

Blue vat dye (obtained by condensing an ANTHRANOL and a QUINONE in boiling nitrobenzene 
with or without oxidizing agent) is mixed with bromin in same solvent and slowly heated to 
boil. More or less Br, and other halogenating agents may be used. Dark green to green black 
powds., insol. in dil acids and alks., sol. in conc. sulf. (BrR-VBr); fast GrEEN vat (V-G) dyes. 

Addition to 1,052,520. 


1,047,812—Dec. 17, 1912. Max H. Isuter, Germany. (Badische.) 


Anthracene dyes and process of making same. 1-Chlor dianthraquinonyl hydrazone, 
and derivs. ‘ 
1-Chlor ANTHRAQUINONE 2-aldehyde or deriy., boiled in naphthalene soln. with ANTHRAQUINONE 
2-hydrazin or deriv. A table of compounds and properties is given. Red powds., sol. in conc. 
sulf. (VR), with boric acid unchanged; orange RED, BLUE to VIOLET vat dye. 


1,047,813—Dec. 17, 1912. Max H. Ister, Germany. (Badische.) 
1.1’/-Dianthraquinonyl-2.2'/-dialdehyde bodies and process of making such 
compounds. 1.1/-Dianthraquinonyl 2.2’-aldehyde with at least one group containing 
nitrogen as NO, or NH,. 
w-Tetrachlor 2.2’-dimethyl 1.1/-DIANTHRAQUINONYL dinitrated, then heated at 125-130° in 
4 parts ninety-nine per cent sulfuric containing 1 part anhyd. boric acid. Or amino derivs. may 
be used. Compounds are diff. sol. in organic solvents when cold, more sol. hot, sol. in conc. sulf. 
(Y-Br); BROWN to gray VIOLET vat (Br-BrR) dyes. 


GROUP III.—ANTHRAQUINONE 51 


1,047,940—Dec. 24, 1912. Max HEssenLAND, Germany. (Hochst.) 
Vat dyestufis of the anthraquinone series and process of making same.—lIn- 
danthrene derivs. 


4-Amino ANTHRAQUINONE 1.2-acridone condensed with 1-chlor ANTHRAQUINONE to form 1- 
anthraquinonyl 4-amino ANTHRAQUINONE 1.2-acridone, product added to fused KOH at 170-180° 
then heated to 210°, diluted and pptd. by air or other oxidizing agent. Dark powds., insol. in 
aq., alc., C,H,, sol. in conc. sulf. (Br-V); Gray to green BROWN vat (Br) dyes. 

Addition to 1,002,270. 


1,050,829—Jan. 21, 1913. Wilhelm Hrrzperc and Walter Bruck, Germany. (Berlin.) 
Anthraquinone vat dye. Anthraquinonyl amino anthraquinone 1.2-phen-acridon and derivs. 
Brominated ANTHRAQUINONE 1.2-acridone or derivs. and 1-amino ANTHRAQUINONE, the beta 
comp. or derivs., boiled in nitrobenzene with copper powd. and a carbonate. Dark violet to 
black powds., insol. in common solvents, sol. in conc. sulf. (Y-G); BRowNn, red BROWN to RED 
vat dyes, fast to washing, Cl and light. 
Addition to 1,008,906. 


1,052,480—Feb. 11, 1913. 
Eduard Hepp, Rudolf Untenuuts and Fritz Roemer, Germany. (Hochst.) 
Dyestuffs of the anthraquinone series and process of making same. An- 
alysis gives C,,H,,N,O,, anthraquinone perazin, etc. 

I.I/-DIANTHRAQUINONYL imid (dianthrimid), or trianthrimid or derivs., condensed in alkali 
or with metallic chlorides, to form dianthraquinonyl INDANTHRENE* which is heated at 80° in 
hypochlorite soln. Yellow to brown red powds., insol. in alks. and acids, diff. sol. in most 
organic solvents, sol. conc. sulf. (VR); YELLOW to ORANGE vat dyes, fast to Cl and alk. 

*Note Wieland, Ber. 4r, 3484 and 43, 999. 


1,052,507—Feb. 11, 1913. Heinrich NERESHEIMER, Germany. (Badische.) 
Vat dyes of the anthraquinone series. Amino anthraquinone acridones, with halogen 
in benzene nucleus. 

Chlor ANTHRAQUINONE acridone, the 2.4-dichlor or other derivs., in nitrobenzene soln., to 
which eighty-seven per cent HNO, is gradually added, and separated product is reduced by alk. 
hydrosulfite to amino comp. Blue to blue green powds., insol. dil. acids and alks., sol. C,H;,NO, 
and C,H,NH, (B-BG), in conc. sulf. (R-Br); BLUE to blue GREEN vat dyes. 


1,052,520—Feb. 11, 1913. Albrecht Scumipt and Georg KranzLEIn, Germany. (Hochst.) 

Condensation products of the anthracene series and process of making same. 
ANTHRANOL or derivs. boiled in nitrobenzene with 1 mol. of a QUINONE or substitution 

product, oxygen being supplied by air, or by components of reaction. Presence of sod. acetate 

to neut. acid and a copper comp. as catalyst facilitates reaction. Table of properties given. 

Cryst. powds. insol. in acids and alks. sol. in conc. sulf. (Y-Br-R); BLUE, GREEN to olive GRAY 

vat (Br-R-V) dyes, fast to washing, bowking, Cl. 
Note 1,046,498. 


¢ 


1,055,287—Mar. 4, 1913. Ditlev Nissen and Erich Saut, Germany. (Cassella, N. Y.) 
Yellow wat dye. (Process also claimed.) 2.3-6.7-Diphthaloyl N-ethyl carbazol or N-ethyl 
dianthraquinonyl mon-azin and derivs. 

N-Ethyl carBazoue or other alkyl deriv., and three parts PHTHALIC anhyd warmed at 50-70° 
in nitrobenzene with AICl, to form N-ethyl carbazole 3.6-DIPHTHALOYLIC acid, and separated, 
purified product heated in conc. sulfuric at 100-105° till insol. in alkali. Yellow powds. or pastes; 
YELLOW vat (Br) dyes, fast to washing, light and Cl. 


1,057,243—Mar. 25, 1913. Max H. Isiter and Paul Nawiasxy, Germany. (Badische.) 
Anthracene coloring-matters and process of making them. [Indanthrene derivs. 
2’-Chlor benzoyl 2-amino ANTHRAQUINONE or derivs., 2 mols., condensed by boiling in nitro- 
benzene or naphthalene containing CuCl, as catalyst and a carbonate to give alk. reaction. 
Products are diff. sol. in usual solvents, sol. in conc. sulf. (B-G), which with HNO, become 
colorless; fast ORANGE to red ORANGE vat dyes. 
Addition to 1,001,408. 


se DIGEST OF PATENTS 


1,058,604—Apr. 8, 1913. Max A. Kunz, Germany. (Badische.) 
Anthracene compounds and process of making them. Pyranthrone 1.2-8.9-di- 

acridone. 

4.4’-Dichlor 2.2/-dimethyl 1.1/-DIANTHRAQUINONYL or derivs. and 2 mols. ANTHRANILIC acid, 
K salt, or other ortho carboxy amino aryl comps., boiled in nitrobenzene with CuO, product 
boiled in ninety-seven per cent sulfuric until color change is complete, and further condensed 
at 140-150° in alc. KOH. The 4.4’-dianthranilo 2.2’-dimethyl 1.1’-dianthraquinonyl is condensed 
at the anthranilo linkage to a diacridone, at the dimethyl dianthraquinonyl linkage to a pyran- 
throne complex. Violet powds., insol. in aq., alks. and acids, sol. in conc. sulf. (R); fast RED 
to VIOLET vat (R) dyes. 


1,059,607—Apr. 22, 1913. Alexander HamMBurGER, Germany. (Bayer.) 
Vat dye. Dibenzoyl 5.5’-diamino 1.1’-dianthraquinonyl thio ether condensed internally whereby 
the carboyl of the anthraquinone loses oxygen and residual carbon forms part of a six mem- 
bered ring containing sulfoxy group. 
Dibenzoyl 5.5/-diamino 1.1’-DIANTHRAQUINONYL thio ether, condensed at ordinary temp. in 
sulfuric acid monohydrate until uniformly blue. Higher temps. split off one or more benzoyl 
groups. Yellow to black powds., sol. conc. sulf. (Br-R-B-G); yELLOW and VARI-COLORED vat dyes. 


1,062,975—May 27, 1913. Max H. Ister, Germany. (Badische.) 
Coloring-matters of the anthraquinone series. (Process also claimed.) 2/-Anthra- 
quinonyl anthraquinone 1.2-imidazole. 
1.2-Diamino ANTHRAQUINONE and dichlor 2-methyl ANTHRAQUINONE boiled in nitrobenzene 
with CuO and an alk. carbonate. Other components are claimed. Products are insol. in aq., 
alks., acids, sol. in conc. sulf. (Y-R); YELLOW, ORANGE to VIOLET vat (OR-BrR) dyes. 


1,062,988—May 27, 1913. Carl Miter and Max H. Isiter, Germany. (Badische.) 
Anthraquinone dye. b-Dianthraquinonyl amidins, containing at least two b-amino anthra- 
quinone residues. 
2-Amino ANTHRAQUINONE or derivs., 2 mols., refluxed in naphthalene with finely divided Cu 
at r100-120°, until uniform, then one mol. carbon tetrachloride added through condenser, and 
further heated at 140-150°. Products are sol. in conc. sulf. (Y-R); YELLOW to orange YELLOW 
vat (Y-R) dyes, fast to light, Cl, soap. 


1,062,990—May 27, 1913. Paul Niawsky, Germany. (Badische.) 
Anthraquinone dyes and process of making them. 1-Oxy 2-methyl 4-anthraquinonyl 
4’-tolyl thio ether or derivs. 
1-Oxy 2-methy] 4-chlor ANTHRAQUINONE or derivs., condensed with 4-thio cRESOL or other 
aryl mercaptan by refluxing in alc. KOH, separated and sulfonated. Orange powds., sol. in aq. 
(O), in conc. sulf. (OR), sol. in alk., which soln. is decol. by hypochlorite, contains more atoms 
of S than K in K salt; yvELLow, ORANGE to RED acid dyes. 


1,063,000—May 27, 1913. Hugo Worf, Germany. (Badische.) 
Anthracene dyes and making the same. Nitro or amino derivs. of iso-dibenzanthrone. 

Iso DIBENZANTHRONE made according to 906,367, warmed to 50-60° in nitrobenzene soln. 
with 2 parts eighty per cent HNO, to form nitro product which may or may not be reduced 
by Na,S. Products are dark powds., sol. in conc. sulf. (G), in boiling C,H;NO, (VB-GB); 


BLUE vat (B) dyes. 
Note 809,892, 818,366, 818,992. Addition to 796,393. 


1,065,102—June 17, 1913. Oscar Batty, Germany. (Badische.) 

Anthracene compounds and coloring-matters and process of making same. 
Anthraquinone 1.2-5.6-dithioxanthones, mono or polyxanthones, and sulfo derivs. 
1.5-Dichlor ANTHRAQUINONE, or other halogen acid substituted deriv., condensed with 2 

mols. thio saLicyLic acid or other ortho thio phenol carbo acid, by boiling in ale. KOH, product 

separated and further condensed in fuming sulfuric acid at common temp., or in other con- 

densing agent with or without a catalyst, then sulfonated or not. Products are insol. in aq., alc., 

alks., sol. in conc. sulf. (R-Y); YELLOW to RED vat dyes or in sulfonated form RED acid dyes. 
Note 1,086,123. 


GROUP III.—ANTHRAQUINONE 53 


1,065,440—June 24, 1913. Hermann FrigEpDMANN, Germany. (Bayer.) 
Dyes of the anthraquinone series. 4’/-Tolyl 2-azimino 3-brom anthraquinone and derivs. 


1-Toluidino 2-amino 3-brom ANTHRAQUINONE, homologs or derivs., treated below 10° with 
HNO, in glac. acetic soln. containing a little sulfuric. Product may be condensed with an amino 
ANTHRAQUINONE by boiling in nitrobenzene with sod. acetate and cupric acetate to form other 
dyes, or may be sulfonated. Products cryst. from C,H,NO, in yellow needles, sol. conc. sulf. 
(CY); YELLOW vat dyes; the sulf. derivs. are YELLOW acid dyes and by condensation with an amino 
anthraquinone are orange RED vat dyes. 


1,067,046—July 8, 1913. Arthur LurrrincHaus and Wilhelm Braren, Germany. (Badische.) 
Anthraquinone acridones, 1.1’-Dianthraquinone acridone and derivs. 


3-Amino 4-methyl pIPHENyL ketone 2/-carboxylic or other, refluxed with 1-chlor ANTHRA- 
QUINONE 2-carbo acid in dil. alk. carbonate soln. containing copper powder, product separated 
and further condensed in conc. sulf. at 100° to an acridone, then by heating to 170° the second 
anthraquinone ring is closed. Red brown to yellow brown powds., diff. sol. in organic solvents; 
fast red ORANGE to yellow ORANGE vat (V) dyes. 


1,070,196—Aug. 12, 1913. Fritz SincER, Germany. (Griesheim.) 
Vat dyes and process of making same. 1-Amino anthraquinone azo imino toluene, and 
derivs. 


1-Amino ANTHRAQUINONE diazotized in conc. sulfuric below 10°, separated and coupled with 
4-TOLUIDIN in acetic soln. Other mono or disazo anthraquinone dyes combined with aromatic 
amins having substituents which prevent coupling in para or ortho positions to amino group are 
claimed. (See list of properties). Brown to yellow red powds., insol. in aq., sol. in C,H,NO, 
(OBr-O), in conc. sulf. (Br-OR); YELLOW to RED vat (BrV-RBr) dyes. 


1,076,249—Oct. 21, 1913. Paul THomascHEwSk1, Germany. (Bayer.) 


Yellow wool-dye of the anthraquinone series. Amino 1-anthra iso thiazole 8-sulfo 
azo aceto-acetanilid, and derivs. 


4-Amino I-ANTHRA ISO THIAZOLE 8-sulfo or derivs., diazotized in conc. sulf. and separated 
product combined in slightly alk. soln. (sod. acetate) with aceto-ACETANILID, or other alifatic beta 
diketones. Yellow powds., sol. in aq. (Y); fast yELLow acid dyes. 


1,076,329—Oct. 21, 1913. Paul THomMascHEWSKI, Germany. (Bayer.) 
Vat dye. 1.2.1’.2’-Dianthraquinonyl thiazins. 


1-Amino 2-brom ANTHRAQUINONE or deriv. and ANTHRAQUINONE 2-mercaptan or deriv. con- 
densed by boiling in nitrobenzene with alk. carbonate. Violet to blue cryst. powds., sol. in 
quinolin (B), in conc. sulf. (G); BLUE vat dyes. 


1,077,115—Oct. 28, 1913. Oscar Batty, Germany. (Badische.) 


Green anthraquinone dyes and process of making them. Nitro or amino derivs. 

of indanthrenes. 

2.2’-Dimethyl 1.1/-DIANTHRAQUINONYL, condensed in nitrobenzene soln. to an INDANTHRENE, 
which is nono or di-nitrated in nitrobenzene soln. with HNO,, then may be reduced by Na,S. 
Products are insol. in acids, alks., sol. in conc. sulf. (BV); Brown vat (G) dyes, color being de- 
veloped by hypochlorite. 

Addition to 856,811. 


1,078,505—Nov. 11, 1913. Wilhelm Herzperc and Gergard Hoppr, Germany. (Berlin.) 


Blue dyes of the anthraquinone series. 1-Amino 4-toluidino anthraquinone 2-carbo 

acid, or derivs. 

1-Amino 4-chlor ANTHRAQUINONE 2-carbo acid or derivs., heated at 100° in autoclave with 
NH, or aromatic amin such as 4-TOLUIDIN, an alk. carbonate and CuSO,. Dark powds., diff. sol. 
aq., easily sol. in alc., glac. acetic, hot C,H,NO,, alks. (B), sol. sixty per cent sulf. (BrR), in one 
hundred per cent sulf. (Br-BrG), in oleum (GB), pptd. on diln. (BrR). When sulfonated are 
blue powds., sol. in usual solvents, sol. in sixty per cent sulf. (R), in oleum and boric acid (B); 
BLUE acid dyes. 


1,079,568—Nov. 25, 1913. A. I. Lasxa and E. J. Ratu, Germany. (Griesheim.) 


Vat dyestuff. (Process claimed.) Two ortho diamino anthraquinones combined by their 
four N atoms with two C atoms of one glyoxylic acid radical to form two five membered 
connecting rings. ’ 


54 DIGEST OF PATENTS 


1.2-Diamino ANTHRAQUINONE, or other ortho diamino derivs., 2 mols. in boiling acetic acid 
soln. to which one mol. GLyoxyLic acid in four per cent soln. is added slowly. Black to blue 
black powds., sol. in conc. sulf. (BrR), not changed by boric acid or HCHO, in sixty per cent 
oleum (V); BLACK to blue BLAcK vat (RBr-BrR) dyes. 

Note 936,565, 1,022,781, and 1,023,248. 


1,086,123—Feb. 3, 1914. Oscar Batty, Germany. (Badische.) 


Anthracene dyes and process of making same. Benzanthrone thio xanthones or 
acridines and derivs. 


1.5-Dichlor BENZANTHRONE boiled in nitrobenzene with 1-2 mols. ANTHRANILIC acid, K_ salt, 
and CuO or other condensing agent. Product may be sulfonated. Other anthraquinone derivs. 
with but one CO intact may be combined with other ortho amino or sulf. hydro derivs. of aro- 
matic carbo acids. Products are insol. in aq., alk., acids, sol. in conc. sulf. (Br-V); RED to 
VIOLET vat dyes, or when sulfonated are RED to VIOLET acid dyes. 
Note 1,065,102. 


1,087,293—Feb. 17, 1914. M. Injinsxi and R. TscHunKeE, Germany. (Wedekind.) 
Yellow vat dyestuffs. 1.2.1’.2'-Dianthraquinone dioxid, the dihalogen and other derivs. 

1-Chlor 2-oxy ANTHRAQUINONE or deriv., 2 mols., heated in iron vessel to 220°, calc. soda 
slowly added and temp. raised to 275°, product separated, purified, and treated with chlorine in 
acid or alk. soln. Yellow powds., sol. conc. sulf. (OR), diff. sol. hot glac. acetic acid and 
C,H,NO,; fast YELLOW vat dyes. 


1,089,221—Mar. 3, 1914. Max H. Ister, Germany. (Badische.)° 
Anthraquinone coloring-matters and process of making them. Composition not 
claimed. 


ANTHRAQUINONE 2-aldehyde, or w-dihalogen methyl derivs., 2 mols. and 1 mol. uR&Ea, or thio 
urea, refluxed in pyridin or quinolin soln. Products are insol. acids, alks., diff. sol. in toluene 
and glac. acetic, sol. in C,H;NO, and conc. sulf. (YBr-R); YELLOW to RED vat (Br-Y) dyes. 


1,090,123—Mar. 10, 1914. : Rene Boun and Carl ImmMERHEISER, Germany. (Badische.) 


Chromium compounds of oxyanthraquinone sulfonic acidS and process of 
making same. Chromium compounds of oxy anthraquinone sulfo acids. 


Hexa oxy ANTHRAQUINONE disulfo, Na salt, (Alizarin Blue BB) boiled in dil. soln. of CrF,. 
Before concentrating silica should be added to fix liberated acid. Other chromium salts and 
other oxy anthraquinones claimed,—see table of properties. With substrata, lakes are formed. 
Products are sol. in aq.; BLUE, RED, GREEN, VIOLET or BROWN acid mordant (Cr) or lake dyes, 
fast to washing, light. 


1,090,621—Mar. 17, 1914. Max H. IsitEr, Germany. (Badische.) 
Anthraquinone vat dyes. Anthraquinone diphenyl dithiazol or other aryl derivs. 


2.6-Diamino ANTHRAQUINONE 1.5-dimercaptan, the 2.7.1.8 or other deriv., condensed with 2 
mols. BENZALDEHYDE, by refluxing in pyridin soln. II. Or a dihalogen diamino anthraquinone and 
benzaldehyde may be condensed in presence of polysulfid to replace H by S or SH. Products 
are yellow powds., insol. dil. acids, alks., sol. in conc. sulf. (OY); YELLOW to yellow ORANGE 
vat dyes. 


1,090,636—Mar. 17, 1914. A. Lutrrincuaus, O. Lousk and A. Sapper, Germany. (Badische.) 
Brown vat dye. Diphenyl 3.4-anthraquinone acridone 3/’.4’-anthraquinone acridin, or di- 
acridone. , 


4-Amino 4’-chlor DIPHENYL or other and 1-chlor ANTHRAQUINONE 2-carbo acid, heated in 
dimethyl anilin soln., separated and heated at 125° in acetic anhyd. and ninety-seven per cent 
sulf. acid to form acridone, which is separated and condensed with 1-amino ANTHRAQUINONE in 
nitrobenzene soln. containing Na,CO, and Cu,Cl,, Another process is described. Product is 
red BROWN vat dye. 5 


1,093,427—Apr. ve 1914. Max H. Isirer and Oscar Batty, Germany. (Badische.) 
Anthraquinone dyes and process of making them. Composition not claimed. 


DIBENZANTHRONE (obtained by fusing benzanthrone with KOH) carefully oxidized in ninety- 
six per cent sulfuric with HNO, or other oxidizing agent, then reduced with bisulfite. Products 
may be sulfonated if desired. Dark powds., insol. in aq., acids, sol. in conc. sulf. (RBr-VR); 
olive GREEN vat (B) dyes, either in oxidized or reduced state. 

Note 809,892 and 1,201,968. 


GROUP III.—ANTHRAQUINONE 55 


1,095,731—May 5, 10914. Filip Kacrer, Germany. (Badische.) 


Producing anthraquinone-thiazoles. Phenyl 1.2-anthraquinone thiazole, dithiazole and 
other derivs. 


2-Amino ANTHRAQUINONE heated in naphthalene, or other solvent, with sulfur and BENzO 
trichlorid to form thiazole. Dithiazole can be formed from beta diamino anthraquinone. Ex- 
amples of other components are given. YELLOW vat dyes (not claimed by patent). 


1,095,780—May 5, 1914. Oscar Batty and Hugo Wo.rFfr, Germany. (Badische.) 
Reddish-brown wat dyes. Phenanthrene quinone 3.4.5.6-dianthraquinone diacridin. 


Dibrom PHENANTHRENE quinone condensed in nitrobenzene soln. with 2 mols. 1-amino an- 
THRAQUINONE and further condensed by heating at 160-165° in ninety-eight per cent sulfuric acid. 
Brown powd., sol. in conc. sulf. (BrR), in twenty-three per cent fuming acid (Br); a red 
BROWN vat (V) dye. 

Addition to 1,016,604. 


1,097,343—May 10, 1914. Bertram Mayer, Switzerland. (Basle.) 
Green vat dyestuffs and process of making same. Nitrated dye of 1,044,797. 
Sulfur vat dyestuff derived from 2-methyl BENZANTHRONE treated with HNO, in mixed acids. 
Dark powds., of metallic luster, insol. in usual solvents, diff. sol. boiling C,H,NO, (G), in conc. 
and fuming sulf. (Br-BrV); GREEN to OLIVE vat (B) dyes. 
Addition to 927,868 and 1,044,797. 


1,103,004—July 7, 1914. Richard Herz, Germany. (Cassella, N. Y.) 


Red vat dyestuffs and process of making same. 2’/-Anthraquinonyl 2”-naphtho- 
quinonyl 1.5-diamino anthraquinone, or other. 
1.5-Diamino ANTHRAQUINONE or other, heated at 60—-100° in glac. acetic soln. with 1.4- 
NAPHTHOQUINONE and separated product condensed with 2-chlor ANTHRAQUINONE, or other, by 
heating in nitrobenzene at 160—-200° with CuCl, and sod. acetate. Brick red to dark red powds., 
insol. acids and alks., diff. sol. in organic solvents; violet RED to RED vat (Br) dyes, fast to wash- 
ing, light, Cl. 


1,123,390—Jan. 5, 1915. K. ScHIRMACHER and A. Voss, Germany. (Hochst.) 
Vat dyestuffs and process of making same. Isatanthrenes. 

1-Chlor ANTHRAQUINONE heated in amyl alcohol with Cu,Cl, and potassium PHENYL glycin, 
amyl alcohol removed and purified product heated with sulfuric acid in ALCOHOL; resulting ethyl 
ester heated at 150° in xylene soln. with caustic alkali in autoclave, separated, and finally treated 
at o° with chlorsulfonic acid, until alk. soln. is nonfluorescent. Products are diff. sol. in aq. 
and inorganic solvents, easily sol. in pyridine (RBr), in conc. sulf. (RV); rEp and VARI-COLORED 
vat (B, etc.) dyes. 


1,126,475—Jan. 26, 1915. Max H. Ister, Germany. (Badische.) 


Yellow to brown vat dyes. Structure is similar to thio indigo, with anthraquinone in- 
stead of phenyl]! rings. 

(a) 1-Chlor acetyl 2-amino ANTHRAQUINONE or other, heated with sulfur in an indifferent 
solvent. (b) Or 2-amino ANTHRAQUINONE mercaptan and oxaLyL chloride, or other, heated 
in dichlor benzene to 180-200°. Yellow to brown powds., containing N and §, insol. in aq., 
acids, alks, sol. conc. sulf. (Y-Br) unchanged by boric acid; fast YELLOW to BROWN vat (V) 
dyes. 


1,128,836—Feb. 16, 1915. Oscar Batuy, Germany. (Badische.) 
Vat dyes. Substituted amino dibenzanthrones. 

Amino DIBENZANTHRONE or iso product prepared as in 796,393, or derivs., heated at 150° 
in autoclave with ETHYL iodide, benzoyl chloride or other alphyl aldehyde or acid deriv. Table 
of properties of products is given. Dark powds., sol. conc. sulf. (BG-BV); RED to blue vIOLET 


vat dyes. 
Note 809,892, 818,992, 906,367, 1,003,268 and 1,063,000. 


1,131,516—Mar. 9, 1915.. W. Herzperc and G. Hopprt, Germany. (Berlin.) 
Greenish-blue dyes of the anthraquinone series. 1-Amino 4-toluidino anthraquinone 


_2-sulfo or derivs. 


1-Amino 4-brom ANTHRAQUINONE 2-sulfo acid, heated with 4-roLu1ipIN or other primary aro- 
matic amin with copper salt as catalyst, with or without agent for fixing halogen acid. Product 


56 DIGEST OF PATENTS 


may be sulfonated to render more soluble. Blue powds., sol. in aq. (GB), which form with HCl 
(VR); green BLUE acid dyes. 


1,133,081—Mar. 23, 1915. Hugo Wo.rr, Germany. (Badische.) 
Production of coloring-matters of the anthraquinone series, (Product claimed.) 
Anthraquinone acridones containing more or less halogen. 
1-Anilino 2-methyl ANTHRAQUINONE or deriv., in 10 parts nitrobenzene, containing a little 
iodine, treated with Cl at 160° until no initial material remains unaltered. Other solvents and 
halogenating agents claimed. Brown red crysts., sol. H,SO, (OR), pptd. on diln. (VR), sol. 
C,H,NO, (VR); fast violet RED vat (VBr) dyes. 


1,139,540—May 18, 1915. G. Kranziein, Germany. (Hoéchst.) 
Arylamino-anthraquinone dyestuffs. 2’-Sulfo 4-methyl 4-anilino 1-amino 2-ethoxy 
anthraquinone, or derivs. 
1-Amino 2-ethoxy 4-brom ANTHRAQUINONE or other amino alkoxy anthraquinone containing 
an acid substituent in para position to the amino group, condensed with 4-ToLUIDIN or other 
aromatic amin, then sulfonated. Products are sol. in aq. (V); vioLET acid dyes, fast to steam- 
ing, alkalies, and but slightly altered by chroming. 


1,150,152—Aug. 17, 1915. Fritz Sincer, Germany. (Griesheim.) 
Process of making alizarin. Alizarin by new process. 

9.10-Dinitro ANTHRACENE, nitro derivs. of 9.10-dihydro ANTHRACENE or other meso nitro 
derivs., heated in autoclave in ag. soln. with NaOH, bisulfite, lime and a nitrate. 

S. 778—‘“‘Alizarin.” 


1,162,496—WNov. 30, 10913. A. I. Lasxa and F. J. Ratu, Germany. (Griesheim.) 


Vat dyes of the anthraquinone series and process of making same. C-Anthra- 
quinonyl N-anthraquinonyl dihydro 1.2-naphthyl thiazin. 
ANILIN azO 2-NAPHTHAYLAMIN, the alfa or beta amino anthraquinone azo 2-naphthylamin 
comps., or other ortho amino azo dyes, condensed with 1-2 mols. ANTHRAQUINONE 2-aldehyde or 
other anthraquinone aldehyde. Yellow, red or brown powds.; ORANGE, RED to BROWN vat dyes. 


1,169,404—Jan. 25, 1916. Max H. Isrner, Germany. (Badische.) 
Blue-gray to green-gray vat dyes. Probably benzanthrone indanthrene. 

Nitro DIBENZANTHRONE or other nitro or amino deriv. of normal or iso comp., heated in 
nitrobenzene soln. with AICI, or other reactive chloride. Dark violet black powds., insol. in aq., 
acids, alks., sol. conc. sulf. (GyV), in C,H;NO,, (BG-RV), in quinolin (GB-BkB); blue Gray 
to green GRAY vat (B) dyes, fast to Cl. 

Addition to 796,393 and 1,063,000. 


1,196, 127—Aug. 29, 1916. Arthur LurrrincHaus, Germany. (Badische.) 
Vat dyes and process of making them. Diphthaloyl carbazoles. 


PutuHatic anhydride, 20 mols., or halogen derivs., condensed with cARBAzoL or deriv., sul- 
fonated and oxidized with hypochlorite. Yellow to orange powds., sol. in conc. sulf. (R-V), in 
sulfonated form sol. in alk. carb. (Y) and are YELLOW acid dyes; in unsulfonated form insol. in 
aq., acids, alks.; yELLOW to orange YELLOW vat (Br) dyes, fast to Cl, light, washing. Dyeings 
with dil. NaOH turn (Br) but color is restored on washing. 

Note 1,055,287. 


1,196,422—Aug. 29, 19016. Max Brcx and Wilhelm Suipa, Aus. Hung. (Hochst.) 
Brown dyestuffs for dyeing wool. 4’-4”-Diamino 3/-3”-disulfo 2.5-dianilino benzo- 
quinone that may be halogenated in benzene nucleus. 

CHLORANIL, benzoquinone or other halogen deriv., ground together with 2 mols. 1.4-PHENY- 
LENE DIAMIN 3-sulfo and sod. acetate then dissolved in aq. at 7o-80°. Dark brown powds., easily 
sol. warm aqg.; BROWN acid or acid mordant (Cr or Cu) dyes, fast to washing and light. 

Note that dye is same class as 1,015,329, etc. 


1,200,848—Oct. 10, 1916. M. Karpos and Paul Nawiasky, Germany. (Badische.) 

Vat dye and process of making it. Composition not claimed, except that at least one 
substituted imid group is present. 
N-Methyl peri-NAPHTHYLAMID (from naphthalene 1.8-dicarbo acid anhydride and methyl 

amin), the unsubstituted comp., acenaphthene quinone oxime or halogen derivs. that may later 


GROUP III.—ANTHRAQUINONE 57 


be treated so as to introduce alkyl or aryl groups in N positions, condensed by boiling to 170- 
230° in caustic alkali, diluted and then oxidized by air. Products may be halogenated. Orange 
red to brown powds., insol. in aq., acids, alks., sol. in conc. sulf. (VR-V); orANcE to red 
VIOLET vat (GB-R) dyes, fast to Cl, light. 


1,201,968—Oct. 17, 1916. Max H. Isier, Germany. (Badische.) 
Vat coloring-matters and process of making them.—Composition not claimed. 


Green vat colors made by oxidizing pDIBENZANTHRONE and derivs. according to 1,093,427 
brominated in nitrobenzene or trichlorbenzene soln. with or without boric acid, in absence of 
oxidizing agent. Green powds., insol. in aq., acid, alks., sol. in conc. sulf. (RV), free of N but 
contain Br.; GREEN vat (B) dyes. 

Note 1,128,836. 


1,202,260—Oct. 24, 1916. Oscar Batty, Germany, (Badische.) 
Vat dyes and process of making them. Substituted amino dibenzanthrones containing 
halogen in nucleus or side chain, or both. 


Amino DIBENZANTHRONE or other product of 1,128,836 or halogen derivs., condensed with 
2-chlor BENZALDEHYDE, product separated then halogenated in nitrobenzene with sulfuryl chloride 
and iodin, or other halogenating agent with or without Beds or carrier. Dark powd., sol. in conc. 
sulf. (B-BV); RED vat dyes. 

Note 1,093,427, 1,201,968, and 1,204,639. 


1,204,639—WNov. 14, 1916. Oscar Batty and Richard Merzcer, Germany. (Badische.) 
Producing vat dyes. Substituted amino dibenzanthrones. 


Nitro DIBENZANTHRONE (Indanthrene Green B paste) or other nitro or amino deriv. of di- 
benzanthrone, boiled with an aldehyde in a soln. of a reducing agent. When FORMALDEHYDE sul- 
foxylate is used both aldehyde and reducing agent are present. Products may be applied to fiber 
from same bath or pptd. by oxidation. No properties given. 

Note 796,393 and 1,202,260. 


1,207,762—Dec. 12, 1916. Max. H. Ister, Germany. (Badische.) 
Anthraquinone dyes and process of making them. Composition not claimed. 


DIBENZANTHRONE oxidized as in 1,093,427, heated in 10 parts 4-TOLUIDIN, or other suitable 
solvent, with a little boric acid or other condensing agent until initial material disappears. Green 
powds., insol. acids and alks., diff. sol. in organic solvents of high b.p.; brown GREEN vat (B) 
dyes, fast to soap and Cl. 


1,207,981—Dec. 12, 1916. Heinrich NERESHEIMER, Germany. (Badische.) 
Anthraquinone dyes and process of making them. 4-Amino 3-sulfo anthraquinone 
4’-chlor phenyl 1.2-acridones, containing one sulfo group only. 


4-Amino 1-brom ANTHRAQUINONE 3-sulfo acid, condensed with 4-chlor ANTHRANILIC acid to 
form 4’-chlor 2’-carboxy 4-anilino 1-amino 3-sulfo ANTHRAQUINONE, and again condensed in 
twenty-three per cent fuming sulfuric acid at 20-25° (mild conditions used to preserve sulfo 
group). Green to blue powds., sol. in ag. (GB), sol. in conc. sulf. ((RBr-Y), insol. in most 
organic solvents; BLUE to GREEN acid dyes which with hydrosulfite split off sulfo group and form 
BLUE vat dyes. 

Note 1,207,982. 


1,207,982—Dec. 12, 1916. Heinrich NERESHEIMER, Germany. (Badische.) 
Anthraquinone dyes and process of making them. 4-Amino 4/-chlor anthraquinone 

phenyl 1.2-acridone, homologs and derivs. 

2'-Carboxy anilino 4-amino 3-sulfo ANTHRAQUINONE or deriv., condensed by heating in chlor 
sulfonic acid as in 1,207,981, again heated in sulfuric acid soln. to remove sulfo group from 
position 3 in the anthraquinone ring. Dark blue powds., containing halogen, insol. in aq., diff. 
sol. in organic solvents of low b. p., sol. hot C,H;NO, (B), in conc. sulf. (Br-Y); green BLUE to 
BLUE vat (V) dyes. 


1,209,163—Dec. 109, 1916. Benno Homo.iKa, Germany. (Hochst.) 
Vat dyestuffe and process of making same. Dimethyl diphenyl diamino benzoquinone, 
or derivs. 


BENZOQUINONE heated in dil. alc. soln. to 40-50° with 2 mols. PHENYL glycin, and when 
CO, ceases to evolve, boiled, filt., etc. Other components and solvents are claimed. Brown 
Sears powds., insol. in usual solvents, sol. conc. sulf. (VR); YELLOW vat (colorless) dyes. 

Note 1,015,329. 


58 DIGEST OF PATENTS 


1,209,212—Dec. 19, 1916. M. P. Scumipt, Germany.(Kalle.) 
Manufacture of vat dyestuffs or initial products of same. Composition not 
claimed. 


3.6-Dichlor 1.4-dianilino BENZOQUINONE (from chloranil and anilin) or other aryl or diaryl 
amino derivs. of halogen benzoquinones, heated in nitrobenzene soln. with copper powder and 
dry sod. acetate or other suitable condensing agents and solvents. Yellow brown powds., sol. 
in C,H,NO, and cone. sulf. (R); YELLOW to BROWN vat dyes. 

Note 1,015,329. 


1,216,134—Feb. 13, 1917. Michael Karpos, Germany. (Badische.) 
Green vat dyes and process of making them. Composition not claimed. 


(a) ACEANTHRENE quinone, halogen or other derivs. condensed with HyDROXYLAMIN to form 
an oxim which is heated in KOH at 210—230°, diluted, acidified with acetic acid and air passed 
through soln. (6) ANTHRACENE 1.9-dicarbo acid imid may be first formed, then fused in caustic 
alkali. Products are GREEN vat (R) dyes. 


1,216,921—Feb. 20, 1917. Oscar Batty and Hugo Wotrr, Germany. (Badische.) 
Yellowish-brown wat dye. Fluorenone dianthraquinone diacridin. 


3.6-Dibrom FLUORENONE, condensed with two mols. 1-amino ANTHRAQUINONE, again condensed 
in sulfuric acid soln. to diacridin. Brown powd., sol. in conc. sulf. (RBr), in twenty-three per 
cent fuming sulf. (Br); yellow Brown vat (RBr) dyes. 

Note 1,016,604. 


1,261,858—Apr. 9, 1918. Maximilian P. Scumipt, Germany. (Kalle.) 


Manufacture of vat dyestuffs of the carbazole naphthoquinone series. (Pro- 
duct also claimed.) 2-or 3-Toluene sulfoxyl 1.4-naphthoquinone 7.8-phen carbazole. 


1.2-Pheno 5-oxy NAPHTHOCARBAZOLE oxidized to a carbazole naphthaquinone, then condensed 
with anilin, TOLUENE sulfinic acid, thio indoxyl or other comp. containing reactive hydrogen, in 
aq. or glac. acetic soln. with or without HCl, finally made alkaline and oxidized. Brown to 
black powds., insol. in aq., diff. sol. in organic solvents; BROWN to BLACK vat (Y-Br.) dyes. 


1,266,896—May 21, 1918. Hugo WotrrF and Filip Kacrr, Germany. (Badische.) 
Anthracene dyes and process of making them. Composition not claimed. 


Acetyl amino ANTHRAQUINONE or derivs., condensed by boiling with POC, or other acid 
chloride and product heated at 140-160° in 15 parts conc. sulfuric, or in same acid chloride, to 
remove aq. Yellow brown to red powds., insol. in aq. alks., sol. in cone. sulf. (RBr-R), in 
boiling glac. acetic and C,H;NO, (Br); red BROWN to yellow BROWN vat (YR-RBr) dyes. 

Note 863,401 and 925,917. 


1,280,648—Oct. 8, 1918. Rene Boun, Germany. (Badische.) 


New anthracene dyes and process of making same. N-Phenyl anthraquinone phen- 
azin, homologs or derivs. 


2-Anilino ANTHRAQUINONE or derivs., added at 180° to ANILIN or other ,aromatic amin con- 
taining KOH, and air passed through soln. at this temp., then sulfonated. Formation of the 
arylamino anthraquinone and above condensation can take place in one operation. Green to 
blue bodies, in unsulfonated form insol. in aq., sol. in organic solvents, and may be employed 
for GREEN to BLUE varnish dyes; in sulfonated form sol. in aq., acids, alks., and GREEN to BLUE 
acid dyes. 


1,285,726—Nov. 26, 1918. Georg KatiscHEer, Germany. 


Anthraquinone derivative and process of making same. 1-Amino anthraquinone 
aryl azo 2-methines, 1-amino anthraquinone 2-aldehydes and derivs. 


1-Amino 2-methyl ANTHRAQUINONE, 2 mols., or 1 mol. of same with 1 mol. of an aromatic 
amin, boiled in nitrobenzene with an alk. carbonate. Treated with acids these products give 
ANTHRAQUINONE 2-aldehyde. Crysts. of metallic luster m.p. 233°, sol. in conc. sulf. (Br), with 
para formaldehyde (B); rEp vat (G-B) dyes. 

Note 1,285,727. 


1,285,727—Nov. 26, 1918. Georg KatiscHer, Germany. 


Vat color and process of making same. 1.1/-Diamino 2-2/-dianthraquinonyl bis-azo 
methine. ‘ 


GROUP III.—ANTHRAQUINONE 59 


1-Amino ANTHRAQUINONE 2-aldehyde of 1,285,726, boiled in glac. acetic to which HYDRAZIN 
hydrate is added. Dark red powd., diff. sol. organic solvents of high b.p., sol. conc. sulf. (BrG) 
which with p-formaldehyde is (GB); fast RED vat (BkV) dye. 


1,317,160—Sept. 30, 1919. Armin Gros and Jakob WurcteEr, Switzerland. (Basle.) 

Process for the manufacture of chlorinated derivatives of the N-dihydro- 
1.2.2’.1/-anthraquinonazin. Di or poly halogen derivs. of N-dihydro 1.2.2’.1/-anthra- 
quinonazin. 


N-Dihydro 1.2.2’.1‘-ANTHRAQUINONAZIN in 4 parts sulfuryl chloride, or other liquid halogen 
comp. other than chlorsulfonic acid, kept at 0° or boiled while current of dry Cl is passed for 
7 hours, or refluxed with excess Cl in boiling POCI, or in liquid Br at 15-20°. A BLUE vat dye, 
fast to Cl. 


1,327,260—Jan. 6, 1920. Alvin S. WHEELER, North Carolina. 
Dyestuffs and process of making same. 2.3.8-Tribrom 5-oxy 1.4-naphthoquinone or 
deriv. 


Jucion, or other oxy naphthoquinone with less than three OH groups, dissolved in 15-20 
parts glac. acetic acid or other solvent, treated with 3-4 parts Br, or Cl and heated by steam 
2-3 hours, then cooled. Products are insol. in aq., sol. in alks.; forming salts which are RED 
direct dyes. 


1,329,435—Feb. 3, 1920. Fritz Srncer and Alfred Hott, Germany. (Chem. Found.) 
Derivatives of pyrazole anthrone yellow. (Process claimed.) Alkyl and dialkyl 
derivs. of dyes of pyrazole anthrone yellow type. 


PYRAZOLE ANTHRONE YELLOW, made by fusion of PYRAZOLE ANTHRONE with alkali, or the nitro 
deriv., digested with fifty per cent KOH until yellow color changes to violet of K salt and 
separated salt as paste heated to 100° in closed vessel with 1-2 parts BENZYL chloride or esters 
of aryl sulfo acids and products further alkylated by same or different agent. Red to brown 
powds., insol. in aq., acids, sol. in conc. sulf. (OQ), rather sol. in hot C,H,NO, and other high 
boiling organic solvents (O); orange RED (mono alkyl derivs.) or BLUE vat (B) dyes. 


1,396,483—Nov. 8, 1921. V. Vi~iicerR and H. von KRANNICHFELDT, Germany. 
Green dyestuff and process of making same. “Trinaphthoquinone and its green re- 

duction product, an inner oxide which has two CO quinone groups reduced to hydroquinone. 

(a) 1.4-NAPHTHOQUINONE heated with water in autoclave at temps. above 100° and product 
freed from hydroquinone. (b) Or the heating may take place in a phenol-aqg. mixture of 120° 
b.p. by refluxing in open vessel. Yellow product is dissolved in 10 parts conc. sulf. at o° and 
zinc dust added. Other non-alkaline reducing agents may be used. Properties of intermediate 
products given. GREEN vat dyes. 


1,419,502—June 13, 1922. Wilhelm Herzperc and Gerhard Hopprt, Germany. (Berlin.) 
Dyes. Composition not claimed. 

Oxy tolu PHENAZIN, obtained by condensation of 2-oxy 5-methyl 1.4-BENZOQUINONE and 1.2- 
diamino BENZENE, or other oxy azin heated at 120° with 2.3-dichlor 1.4-NAPHTHOQUINONE or other 
nucleus substituted halogen quinonoid comp., in presence of anhyd. sod. acetate and Cu,Cl,. 
Yellow to orange crysts., diff. sol. organic solvents, sol. in conc. sulf. (OR-R); YELLOW to 
ORANGE vat dyes fast to Cl and soap. 


1,430,277—Sep.t 26, 1922. Frederich W. Atack and John AnpbErRson, England. (British Aliz.) 
Fusion of organic substances with alkalies. Various indanthrenes. 


2-Amino ANTHRAQUINONE is fused with caustic in presence of an inert nonhydroxylic diluent 
such as anilin, naphthalene, paraffin, etc., at suitable temps. BLUE to GREEN reducing vat dyes. 


1,431,656—Oct. 10, 1922. Wilhelm Herzserc and Gerhard Hoppr, Germany. (Berlin.) 
Dye. Composition not claimed. 
NAPHSULTAM 3.4-PHENAZIN, heated at 120-140° with CHLORANIL or other halogen quinone 


deriv., in nitrobenzene soln. containing sod. acetate. Yellow to orange crysts. or powds., diif. 
sol. organic solvents, sol. in conc. sulf. (OR); YELLOW to ORANGE vat dyes, fast to Cl and soap. 


1,437,783—Dec. 5, 1922. 
Ewald Srernpacu, Franz ACKERMANN and Max UvrzincER, Switzerland. (Basle.) 
Manufacture of condensation products of the anthraquinone series. (Product 
also claimed.) : 
5 


60 DIGEST OF PATENTS 


1-AminoO ANTHRAQUINONE or deriv. in nitrobenzene soln. is heated at 130° with cyYANURIC 
chloride or other 1.3.5-triazin halogenated in the nucleus. Other solvents and temps., catalysts 
such as Cu,Cl, with sod. acetate, etc., as neutralizing agent, and a large number of derivs. are 
claimed, and further condensations are made. Vari-coLorED reducing vat dyes. (Not claimed.) 


1,446,163—Feb. 20, 1923. Arthur H. Davies, England. (Scottish Dyes.) 
Manufacture of oxy derivatives of anthraquinone. Alizarin or other oxy deriva- 
tives of anthraquinone. 


2-Chlor ANTHRAQUINONE with 3.5 parts NaOH, 0.14 parts NaClO, or other oxidizing agent, 
and 11 parts aq. is heated at 170° for 24 hours in an autoclave. Rep acid mordant dyes. 


1,451,270—Apr. 10, 1923. William J. Port, England. (Scottish Dyes.) 
Production of coloring matters. Increased yield of indanthrene, or other anthraquinone 
azin. 


2-Amino ANTHRAQUINONE or deriv. is heated at suitable temp. with fused KOH in presence 
of potassium formate, acetate, etc., or mixture of these or other appropriate organic salt with or 
without an inert diluent, then oxidized to the dye. Or an oxidizing agent may be added to the 
melt to further improve yields. Brug reducing vat dyes. 


1,452,774—Apr. 24, 1923. Frederick W. Aracx, England, and Charles W. Sourar, Scotland. 


Intermediates and dyestufis of the anthraquinone series. 3.3’-Dichlor in- 
danthrene. 


2-Amino 1-brom 3-chlor ANTHRAQUINONE with 0.5 parts fused sod. acetate and 0.3 parts cryst. 
Cu acetate are boiled in 12 parts nitrobenzene until no further dye forms. The process for 
making chlor, then brom chlor amino anthraquinone and the dye may be made continuous. BLuE 
reducing vat dye. 


1,459,536—June 19, 1923. Filip Kacer, Germany. (Badische.) 
Manufacture of vat coloring matters. (Product also claimed.) Tere phthaloyl di- 
anthraquinone 1.2.2’.1'-dithiazole. 


1-Mercapto 2-amino ANTHRAQUINONE or deriv. and 0.4 parts tere PHTHALOYL chloride are 
boiled in 10 parts nitrobenzene. Fused with alkali product becomes N-dihydro anthraquinone 
azin. w-Tetra or hexachlor 4-xYLENE heated with sulfur and 2-amino ANTHRAQUINONE produce the 
same dye. Any aromatic comp. containing two reactive carbon atoms such as carbo or aldehyde 
carbonyl chloride, di or tri halogen methyl groups, etc., may be used like phthaloyl chloride. 
Yellow powds., sol. conc. H,SO, (V); YELLow reducing vat (V) dyes. 


1,464,079—Aug. 7, 1923. Max A. Kunz, Germany. (Badische.) 
Production of vat coloring matters. (Product also claimed.) 


DIBENZANTHRONE and 0.39 parts HYDROXYLAMIN sulfate in 20 parts H,SO, (66°) are heated 
at 165-170° for 2-3 hours. Copperas may be added and electrolytically reduced HNO, em- 
ployed instead of hydroxylamin. Dyes are insol. in organic solvents except boiling pyridin (B 
with R fluor), sol. conc. H,SO, (V) with formaldehyde (more B) with HNO, (B-BG); blue 
GRAY to dark gray to blue BLAcK reducing vat (V) dyes. 

Note 818,992. 


1,464,598—Aug. 14, 1923. Lloyd C. DanrEts, New York. (National.) 
Production of vat dyestuffs. Purified nitrodibenzanthrone dyes. 


DIBENZANTHRONE that has been freed of impurities insol. in alk, hydrosulfite is dissolved in 
6 parts nitrobenzene at 50-60° and o.8 parts HNO, (eighty per cent) (1.46 sp. gr.) slowly added 
during 1-1.5 hours then kept at same temp. 2-3 hours, cooled to 20-25°, slight excess Na,CO, 
and 6 parts aq. added and solvent removed by steam, etc. Dark violet powds., insol. aq. and 
dil. acids, alks.; blue to yellow GREEN reducing vat (B) dyes. 


1,478,027—Dec. 18, 1923. Lloyd C. DaniEeis and Winthrop S. Lawrence, New York. (National.) 


Production of wat dyestuffs. (Product also claimed.) Purification and isolation of ben- 
zanthrone dyes. 


Mineral o1, of b.p. 230°, 4.2 parts mixed with 1 part KOH, is heated to 215~-230°, 0.24 
part dextrin then 1 part sublimed BENZANTHRONE added and temp. maintained until reaction is 
complete. Product is blown into large vol. aq. containing two per cent NaOH and two-tenths per 
cent bisulfite to protect from oxidation. The kerosene will form an air protecting layer and 
the alkali will dissolve the purified dye. Soln. is heated to 60-70°, filtered to remove insol. 


GROUP IV.—AURAMIN 65 


impurities, and dye pptd. by aeration. Nonvatable impurities also possess dyeing properties. 
GREEN reducing vat dyes. 


1,478,061—Dec. 18, 1923. Donald G. Rocers and Harold T. StowrLi, New York. (National.) 


Vat dye. (Process also claimed.) Improved process for flayanthrone (Indanthrene Yellow 

G) and intermediate product. 

One part powd. 2-amino ANTHRAQUINONE (one hundred per cent basis) suspended in 12 parts 
nitrobenzene at usual temp. to which are slowly added 3.5 parts SbCl;. Temp. rises to 60-75° 
and is further raised to 145-150° for 45 m., slowly cooled to 35° and resulting compound of dye 
with SbCl, filtered off, purified by treatment with fresh nitrobenzene at 100°, etc. Product is 
hydrolyzed by dissolving at usual temp. in 66° sulf. acid and pouring into 30 parts aq. Comp. 
of SbCl; and dye is claimed. YxELLow reducing vat dye. 


Group IV.—AURAMIN. 


301,802—July 8, 1884. H. Caro, Germany, and A. Kern, Switzerland. (Badische.) 


Manufacture of yellow coloring-matter. (Product, not process, claimed.) Tetra 
methyl diamino benzophenone imid. 
Tetra methyl diamino BENZOPHENONE heated to 180° with NH,Cl and ZnCl,. A YELLOW 


basic mordant dye. 
S. 493—‘‘Auramin.” 


488,430—Dec. 20, 1892. R. GneuM and J. Scumip, Switzerland. (Basle.) 
Basic yellow dye. sym-Dimethyl 4.4’-diamino 3.3’-dimethyl benzophenone imid. 


Methyl 2-tonup1n, 2 mols., heated in acid soln. with 1 mol. FORMALDEHYDE to form sym- 
dimethyl 4.4’-diamino 3.3’-dimethyl BENZOPHENONE then heated to 175° in admixture with § 
and NH,Cl, while dry NH, gas is passed in. A YELLOW basic mordant dye. 

S. 494—“‘Auramin G.” Note 301,802. 


689,025—Dec. 17, 1901. F. RunKet, Germany. (Elberfeld.) 
Basic red-violet dye and process of making same. An imino substituted auramin. 


AvurRAMIN G, homologs or thio derivs., heated in thirty per cent HCl with N.2-dimethyl 
INDOLE, or other. A vioLET basic mordant dye, fast to acids and alks. 
Addition to 677,279. 


720,920—Feb. 17, 1903. ‘C. Horrmann, Germany. (Hochst.) 
Alkylated auramins and process of making same. An alkyl or aryl substituted 
auramin. 


AURAMIN base heated in xylene or other soln. with calcined MgO, or other, and BENZYL 
chloride, or other. A YELLOW to green-YELLOW basic mordant dye, faster to soap or soda than 
auramin dye. 

S. 493—‘‘Auramin.” 


Group V.—AZIN, including INDULIN. 


82,129—Sept. 15, 1868. Jean Lamsert, Jr., New York. (Jean Lambert and Chas. Rumpff.) 
Improved aniline-dye. (Process also claimed.) Basic red dye called ‘‘Saffranine Red.”’ 


Mauveine, or Perkins Violet, derived by oxidation of a salt of ANILIN with bichromate, 
hypochlorite, permanganate, etc., is dissolved in 2 parts 8° acetic acid in 100 parts aq., and 
boiled with PbO, or other oxidizing agent, unchanged violet pptd. by excess alkali, filt. and 
saffranine red in soln. salted out or pptd. with tannin, etc. A basic RED dye. 

Near S. 679—‘‘Safranin.”’ 


248,246—Oct. 11, 1881. Orto N. Wirt, Germany. (Cassella.) 
Coloring-matter. Dimethyl 4’-amino 2-anilino 3-amino dimethyl 6-amino-phenazin. 


Nitroso dimethyl anrtnin HCl and one mol. 3-PHENYLENE DIAMIN mixed in aq. soln. heated 
with steam to boil and HCl in excess added with or without an oxidizing agent such as air or 
FeCl,. Ingredients may be made to react in dry condition also. A viotEeT basic and basic 
mordant dye. 

S$. 669—“‘Neutral Violet, extra,”’ and S. 678, “Fast Neutral Violet B.” 


62 DIGEST OF PATENTS 


249,136—Nov. 1, 1881. Otto N. Wirt, Germany. (Cassella.) 


Production of coloring-matter. (Product, not process, claimed.) 2-Methyl 3-amino 
dimethyl 6-amino phenazin. 
Nitroso dimethyl anrt1n HCl mixed in aq. soln. with one mol. 3-TOLUYLENE DIAMIN, boiled, 
HCl added with or without air or FeCl, etc. Or components may react dry. Rep basic dye. 
S. 670—“‘Neutral Red, extra.” Homolog of 248,246. 


369,764—Sept. 13, 1887. Joseph ANNAHEIM, Switzerland. (Durand.) 


Manufacture of blue coloring-matter. (Product also claimed.) N-Tolyl 2-toluidino 
dimethyl isorosindulin. 

Diphenyl NAPHTHALENE DIAMIN, or homolog, condensed with nitroso dimethyl aninin HCl 
by heating in weak aq., alk., neut. or acid soln., in glac. acetic or alc. solns. Or the nitroso 
dimethyl anilin can be reduced with Zn and HCl, then condensed with dioxy naphthalene, and 
product oxidized with bichromate, etc. 

S. 677—“Basle Blue R.” 


392,723—Nov. 13, 1888. Emil Ersarsser, Germany. (Dahl.) 
Blue coloring-matter obtained from paraphenylen-diamine, etc. 

Amino azo BENZENE HCl, or derivs., mixed with equal parts 4-PHENYLENE DIAMIN, or other, 
heated in closed vessel at 140-185° with strong agitation and dye separated as HCl salt. Bus 
direct, basic mordant and developed (CrO,) dyes, fast to light and when chromed also fast to 
washing. 

S. 701—‘‘Paraphenylene Blue R.”? Note 524,677. 


395,300—Dec. 25, 1888. : Arthur WeEINnBERc, Germany. (Cassella.) 
Blue coloring-matter from nitroso derivatives upon phenylene-diamines. 
Dimethyl phenyl safranin and dimethyl amino anilino deriv. 
Diphenyl 3-PHENYLENE DIAMIN, or homologs, heated in alc. soln. with one mol. nitroso dimethyl 
ANILIN HCl. Less of nitroso comp. gives product more violet shade. BuLuE basic and basic 


mordant dye. 
S. 689—‘“‘Indazin M.,”? S. 691, ‘‘Metaphenylene Blue B.” Homolog of 248,246 and 249,136. 


420,311—Jan. 28, 1890. Alcide F. Porrrier, France. 
Nitroso dye. Probably tetramethyl 2.6-diamino phenazin. 

4-Nitroso dimethyl anit1In HCl, or other secondary or tertiary amin or deriv. boiled in 5 
parts aq. for 3 hours, or boiled in organic solvents such as alc., benzene, etc., then pptd. by 
ZnCl,. Brown powds., sol. in aq., alc. and acids, pptd. by alks. and alk. carbonates; Gray to 
BROWN basic and basic mordant dyes, fast to soap, air, light and adapted to printing. Patent 
also in Group X because of title, though in fact an azin dye. 

S. 681—‘“‘Methylene Gray O.” 


428,530—May 20, 1800. Conrad Scurause, Germany. (Badische.) 
Rosinduline monosulpho-acid. (Process also claimed.) Mono sulfo phenyl rosindulin. 


ANILIN azO NAPHTHALAMIN HCl, or other, condensed at 140-170°, with 1 part ANILIN HCl 
and 3.5 parts ANILIN to form phenyl ROSINDULIN, purified, base separated, and monosulfonated. 


Violet RED acid dyes. 
S. 672—“‘Azocarmin G.” Note 430,975 for disulfonated dye. 


430,975—June 24, 1800. Conrad ScHrause, Germany. (Badische.) 
Red dye. Rosindulin disulfo acid. 


Mono sulfo phenyl ROSINDULIN, prepared as in 428,530, or the unsulfonated base, mixed with 
3 parts fuming (twenty-three per cent SO,) H,SO, at 0°, then heated at 40° till sol. in aq. 
(disulfo deriv.) RED acid dye. . 
S. 672—“‘Azocarmin G.”’ 


431,404—July 1, 1809. Conrad ScurausE, Germany. (Badische.) 
Rosinduline sulpho-aecid. Sulfonated rosindulin, not disulfo deriv. 


Phenyl rostnpULIN sulfo added to 6 parts fuming H,SO, (twenty-three per cent SO,), keep- 
ing well cooled, then heated to 100° till sol. in aq. RED acid dye. 
S. 672—“‘Azocarmin G.” 


GROUP V.—AZIN 63 


443,40S8—Dec. 23, 1890. Conrad Scuraust, Germany. (Badische.) 
Yellow red-dye. Probably the mono sulfo acid of rosindone. 


RostnDULIN sulfo acid made as in 431,404, mixed with 15 parts seventy-five per cent H,SO,, 
refluxed 16 hours until insol. in aq. and of orange-red shade, dissolved in boiling dil. NaOH and 
repptd. by acid. Orange-rEp acid dyes. 

Probably S. 674 and 675—“Rosindulin G and 2 G,” credited to Hepp, 1890. Note 428,530 
and 430,975. 


458,281 Aug. 25, 1891. Benno Homouxka, Germany. (Hoéchst.) 
Induline dye. (Process also claimed.) 


Mixture of alcohol soluble indulin produced as in 418,916 (A), 2 parts, and 0.44 parts 4- 
PHENYLENE DIAMIN HCl are added to 3 parts melted 4-PITENYLENE DIAMIN, with or without one 
per cent BENzorIc acid as accelerator, and heated at 150-180° according to shade desired until com- 
pletely sol. in dil HCl. Shade becomes more gray with rise of temp. above 150°. Blue vioLET 
to BLUE direct and basic mordant dyes, fast to washing and light. 

S. 7o2—‘‘Para Blue” (probably). 


466,826—Jan. 12, 1802. Eduard Hepp, Germany. 
Blue-red dye. Phenyl rosindulin trisulfo acid. 
Phenyl RosINDULIN added to 3 parts fuming H,SO, (thirty per cent SO,) and heated at 100° 


until aq. sol. Rep acid dye. 
S. 673—“‘Azocarmin B.” 


466,852—Jan. 12, 1892. Eduard Hepp, Germany. (Kalle.) 
Disulpho-acid of phenyl-rosinduline. Phenyl rosindulin beta disulfo acid. 


Phenyl rosinpuLIN heated at 170° in 15 parts conc. H,SO, for 12 hours or until aq. sol. 
Violet RED acid dye. 

S. 672—‘“‘Azocarmin G” (probably). Note 430,975 for another disulfo acid and tests to dis- 
tinguish the two. 


491,378—Feb. 7, 1893. Jakob Scumip and Johannes Mouter, Switzerland. (Basle.) 


Violet-blue induline dye. (Process also claimed.) Amino N-phenyl 5.4’-diamino rosin- 
dulin (probably). 
4-PHENYLENE DIAMIN HCl and 2.5-3 parts 4-PHENYLENE DIAMIN heated at 160-165°, and 
within 2 hours 1 part 4-nitro I-NAPHTHYLAMIN, or isomer is added, NH, and H,O are liberated. 
Temp. is kept at 180—-190° till test sample with HCl is blue-violet shade. Violet sLuxE direct and 
basic mordant dyes, fast to light and washing. 


511,653—Dec. 26, 1893. Gustav ScuuLtz, Germany. (Berlin.) 
Blue dye. (Process also claimed.) as-Dimethyl ditolyl safranin. 


as-Dimethyl 4-PHENYLENE DIAMIN HCl, derived by reduction of nitreso comp. with Zn and 
HCl in alc. soln., 4.4’-ditolyl 3-PHENYLENE DIAMIN, or homolog, 1 mol. each, are heated in alc. 
soln. to 70°, conc. soln. of bichromate added and boiled 1 hour. Other asymmetrical mono or 
di alkyl para diamins are claimed. Violet BLUE basic mordant dye. 

S. 690—‘“‘Metaphenylene Blue R.” 


524,222—Aug. 7, 1894. Conrad ScurausE and Eugen Romic, Germany. (Badische.) 
Violet-red dye. Disulfo acid of phenyl rosindulin. 


2-Amino 4-sulfo DIPHENYLAMIN condensed by boiling in alc. soln. with oxy NAPHTHOQUINONE 
anil to a phenyl ROSINDULIN mono sulfo acid and product sulfonated in 4 parts ninety-five per 
cent H,SO, at 100° or second sulfo group can be introduced by using a sulfo acid of the 
naphthoquinone comp. Violet-rEp acid dye. 

Isomer of S. 672—‘‘Azocarmin G.’’ Note isomeric product 430,975. 


524,677—Aug. 14, 1894. Emil Exsargsser, Germany. (Dahl.) 
Blue-dye. (Process also claimed.) as-Disulfo 2’-naphthyl amino phenyl dimethyl rosindulin. 

Disulfo 2.2’-dinaphthyl 3-PHENYLENE DIAMIN, 1 mol., condensed at 5-10° in thirty per cent 
acetic acid containing sod. acetate, with nitroso dimethyl anit1n HCl, neut. with soda, heated 
to 60-70° and salted out. Or dimethyl amino azo BENZEN& or its sulfo acid can be used as second 
component with temp. of 90-100°. BLuk acid dyes. 


64 DIGEST OF PATENTS 


533,829—Feb. 5, 1895. Conrad ScHrausr, Germany. (Badische.) 
Red basic dye. (Process also claimed.) 2-Alkyl eurhodin. 

SULFANILIC acid azo alkyl 4-TOoLUIDIN in phenol soln., heated to 95° and one mol. 1- 
NAPHTHYLAMIN HCl added, cooled, excess phenol removed with NaOH, etc. Orange-rEp basic 


mordant dye. 
S. 671—“Indulin Scarlet.” 


536,626—Apr. 2, 1805. Robert Hirsu, Germany. (St. Denis.) 
Blue dye. (Process also claimed.) Tetra methyl 3.7-diamino phenazin and homologs. 
Nitroso dimethyl an1L1n reduced in aq. soln. at 40° with Zn., soln. neut. with Na,CO,, 
filt., and amino comp. oxidized in boiling acid soln. by slowly adding bichromate mixed with 
excess acid. Dye is pptd. with ZnCl,. BLur or BLacx basic mordant dye. <A by-product of the 
reaction is a gray-VIOLET basic or basic mordant dye. 
S. 681—‘“‘Methylene Gray O” deriv. Note 420,311. 


543,784—July 30, 1805. Conrad Scuraust, Germany. (Badische.) 
Yellow dye. (Process also claimed.) N-Phenyl phenanthro phenazin. 

2-Amino DIPHENYLAMIN, I mol. and 1 mol. PHENANTHRENE QUINONE heated in 20 parts glac. 
acetic to 100° till test with boiling HCl shows that reaction is complete, diluted with HCl, filt. and 
pptd. by ZnCl,. A YELLOW basic mordant dye. 

Near S. 684—‘“‘Rhodulin Violet.” 


5643,894—Aug. 6, 1805. Rudolf Rryuer, Germany. (Bayer.) 
Azin dye and process of making same. N-Phenyl 2-methyl 3-amino dimethyl 6-amino 
phenazin. 


Phenyl 3-TOLUYLENE DIAMIN, or derivs., mixed in alc. soln. with 1 mol. nitroso dimethyl 
ANILIN, or homolog, stirred till color is blue, then refluxed until of red color. R&p basic mordant 
dyes, fast to washing and light. 

Near S. 684—‘‘Rhodulin Violet.”” Note 543,894 and 550,062. 


557,022—Mar. 24, 18096. Rudolf Rrtyuer, Germany. (Bayer.) 
Azine dye. (Process also claimed.) N-Phenyl 2.5-dimethyl 3-amino methyl 6-amino phenazin 

and homologs. 

Phenyl 3-ToLUYLENE DIAMIN mixed in alc. soln. with one mol. nitroso methyl 2-ToLuIDIN, 
then refluxed until of red color. Rep basic mordant dyes, fast to washing and light. 

Near S. 684—“‘Rhodulin Violet.” Note 543,894 and 559,062. 


559,062—Apr. 28, 1896. Rudolf Reyuer, Germany. (Bayer.) 
Azin dye and process of making it. N.4’-Tolyl 2.5-dimethyl 3-amino methyl 6-amino 
phenazin. 


4'-Tolyl 3-TOLUYLENE DIAMIN mixed in alc. soln. with 1 mol. nitroso methyl 2-TtoLuipiIn HCl 
then refluxed until of red color. Rep basic mordant dyes, fast to alk. and light. 
Near S. 684—“Rhodulin Violet.” Note homolog in 543,894, 557,022, etc. 


559,063—Apr. 28, 1896. Rudolf Reyuer, Germany. (Bayer.) 
Azin dye and process of making it. N-4/-Tolyl 2.5-dimethyl 3-amino dimethyl 6-amino 
phenazin. 


Same process as 559,062, using nitroso dimethyl ANILIN instead of mono methyl deriv. 
Violet-RED basic mordant dye. 
S. 684—“‘Rhodulin Violet.” 


567,473—Sept. 8, 1896. Wilhelm Herzserc and Heinrich Hermann, Germany. (Berlin.) 
Red dye of rosindulin series. Trisulfo acid of phenyl rosindulin. 

I-NAPHTHYLAMIN and equimol. of 2-aming DIPHENYLAMIN sulfo are mixed in dil. HCl soln. 
to which bichromate is added. Separated rosindulin monosulfo acid is heated at 165-170° with 
3 parts ANILIN and 0.5 part ANILIN HCl and resulting phenyl rostnpULIN sulfo acid further 
sulfonated by heating at 65-70° with 3 parts fuming H,SO, (thirty-two per cent SO,). Violet- 
RED acid dyes, fast to light and alks. 

S. 673—“‘Azocarmin B.” 


GROUP V.—AZIN 65 


578,093—Mar. 2, 1897. Albert CospgenzL, Germany. (Hochst.) 
Blue dye. (Process also claimed.) 4’-Amino anilino deriv. of diethyl safranin. 

Diethyl SAFRANIN, derived from diethyl 4-PHENYLENE DIAMIN and ANILIN, heated in closed 
vessel under pressure for 4-5 hours at 180° with one mol. 4-phenylene diamin until red violet 
color disappears, dissolved in dil. HCl and pptd. by ZnCl, or a weak alkali. Buug basic dye 
adapted for printing, fast to light and alkalies. 

Near S. 689—‘“‘Indazin M.’”? Note 395,300. 


588,397—Aug. 17, 1897. | Albert CopenzL, Germany. (Héchst.> 
Gray dye. (Process also claimed.) Probably an intramolecular condensation of safranin 
and formaldehyde. 
Dimethyl saAFRANIN, or homologs, condensed in 2 parts conc. HCl with 1 part FORMALDEHYDE 
(forty per cent) by heating at 100°, soln. diluted and pptd. by ZnCl,. Gray basic mordant dyes, 
fast to soap and alk. 


592,608—Oct. 26, 1897. Bernard Heymann and Rudolf Reyvurr, Germany. (Bayer.) 
Red azin dye. (Process also claimed.) Ethyl tolu safranin and derivs. 

4-Amino ethyl 2-toluidin HCl (ethyl 3-roLtuyLENE DIAMIN) and ethyl 2-TOLUIDIN, 1 mol. each 
in aq. soln. and to this at common temp. is slowly added a soln. of bichromate to condense to 
an INDAMIN. More bichromate and one mol. ANILIN are added, mixture boiled and dye filtered 
out and purified. Rep basic or basic mordant dyes, fast to alk. and light. 

S. 684—“‘Brill. Rhodulin Red B.” 


602,544—Apr. 19, 1808. Philip Orr and Thilo Krorser, Germany. (Elberfeld.) 
Blue azin dye. (Process also claimed.) N-Phenyl dimethyl 2-amino 4.8-disulfo 9-phenyl 
imino rosindulin. 
sym-Diphenyl 1.3-NAPHTHALENE DIAMIN 8-sulfo acid, or derivs., 1.5 mols., and 1 mol. 
dimethyl 4-amino DIPHENYLAMIN 2-sulfo are heated in amyl alc. at 100-130°. Homologs and 
derivs. claimed. Buivus acid dyes, fast to acids, alks., and rather fast to light. 


603,013—Apr. 26, 1808. Philip Orr and Thilo Krorsrer, Germany. (Elberfeld.) 
Blue azin dye. (Process also claimed.) N-Phenyl ethyl 4/-sulfo benzyl 2-amino 8-sulfo 
g-phenyl imino rosindulin. 
sym-Diphenyl NAPHTHALENE DIAMIN 8-sulfo, or derivs., dissolved at 80° in abs. alc. containing 
sod. acetate and one mol. 4-nitroso ethyl 4’-sulfo benzyl aniL1In and more alcohol slowly added. 
BuveE acid dyes, fast to acids, alks. and somewhat fast to light. 


606,295—June 28, 1808. Philip Orr and Thilo Krorser, Germany. (Elberfeld.) 
Blue-azin dye and process of making same. N-Phenyl phenyl 2-amino 3.8-disulfo 
9-phenyl imino rosindulin. 
sym-Diphenyl 1.3-NAPHTHALENE DIAMIN 8-sulfo acid and 4-amino DIPHENYLAMIN 2-sulfo, 1 
mol. each, dissolved in strong alc. containing sod. acetate heated at 82-85° and soln. of bichro- 
mate slowly added. Homologs and 6-sulfo derivs. are claimed, and other oxidizing agents. 
BuveE acid dyes, fast to acids, alks. and milling. 


609,352—Aug. 16, 1808. Paul Junius, Germany. (Badische.) 
Blue dye. (Process also claimed.) Diethyl 2-amino oxy 8-sulfo rosindulin. 
Nitroso diethyl 3-amino PHENOL, or other, condensed in sixty per cent acetic acid at 100° 


with 1 mol. 1-NAPHTHYLAMIN 6- or 7-sulfo acid in presence of sod. acetate. BLug acid dye, fast 
to alks. 


617,703—Jan. 10, 1899. Wilhelm Urrrserc and Henrich Hrimann, Germany. 
Blue safranin dye. (Process also claimed.) N-Phenyl dimethyl 2-amino 4’-dimethyl amino 
phenyl 9-imino rosindulin. 

Neutral Blue, derived from nitroso dimethyl ANILIN and phenyl 2-NAPHTHYLAMIN oF 
homologs, heated with 1 part bisulfite in 5 parts aq. at 100°, until brown color is pptd. and soln. 
nearly colorless, then 1.5 parts HCl added and again heated at 100°. Resulting 9-sulfo acid is 
dissolved in 10 parts alc. and 1.5 parts dimethyl 4-PHENYLENE DIAMIN added and boiled until 
SO, ceases to escape. Biux basic mordant dyes, fast to light and washing, adapted for 
printing. 


66 DIGEST OF PATENTS 


673,640—May 7, 1901. Arnold Hess, Germany. (H6chst.) 
Blue wool dye and process of making same. 


1.5-Dinitro NAPHTHALENE heated in chlor sulfo acid soln. with H,S to 70-90° when vigorous 
reaction sets in and temp. rises to 130-140°. ‘Temp. is reduced and kept at 110-1209 for some 
hours while H,S is passed in. Biur and Gray acid and developed (CrO,) dyes, which when 
chromed are fast. 


726,667—Apr. 28, 1903. Emil A. Fourngaux, New York City. (Metz.) 
Blue basie dye and process of making same. 


as-Dimethyl or diethyl PHENOSAFRANIN (Methylene Violet 3RA) derived by oxidation of 
dimethyl 4-PHENYLENE DIAMIN and ANILIN, diazotized with o.5 mol. NaNO,, soln. nearly or 
quite neut. with NaOH and let stand 1 day. Soln. is made acid with acetic, boiled, and dye pptd. 
by ZnCl, and NaCl. Brug basic dye. 


872,815—Dec. 3, 1907. Heinrich Heimann, Germany. (Berlin.) 
Safranin dye and process of making same. 4’-Sulfo N-phenyl ethyl 4”-sulfo benzyl 

2-amino 4”’-amino 2”’-sulfo phenyl 7-imino phenazin. 

4-Nitro 4'/-amino DIPHENYLAMIN 2-sulfo, Na salt, and ethyl 4’-sulfo benzyl aniiin, Na salt, 
in aq. soln. are treated with soln. of bichromate and HCl and when InpAMIN has formed more 
bichromate and suLFANILIC acid are added and the mixture warmed till clear red-violet color. 
Resulting nitro comp. is reduced in HCl soln. by Fe to amino deriv. shown by blue color. . 
BuvE acid dye. 


900,302—Oct. 6, 1908. Adriano Ostrocovicu, Roumania, and Theophile SILBeERMANN, Germany. 
Process of producing indulin colors. Producing indulins by use of halogen instead 
of acid for condensation. 


ANILIN and iodin, equal parts, are mixed and as temp. rises to 70° heat is applied, at 100° 
mass thickens and at 140° crystallizes. At 180° reaction ceases, but temp. is maintained for 
short time. When chlorine is halogen used, several methods may be employed. PbO, and 
anilin HCl or di-iodo ethylene, etc., may also be used. 

S. 697—‘‘Fast Blue, sp. sol.’”’ or “Indulin, sp. sol.’ 


940,354—Nov. 16, 1909. Philip Orr, Germany. (Bayer.) 
Azin dye and process of making same. N-Phenyl 4’-amino sulfo phenyl 2-amino 
3-methoxy 8-sulfo 9-phenyl imino rosindulin. 


sym-Diphenyl 1.3-NAPHTHALENE DIAMIN 8-sulfo acid, isomers or homologs, and 4-amino 2’- 
methoxy amino DIPHENYLAMIN sulfo, 1 mol. each in alc. soln. containing Na,CO,, heated to 30- 
50° with ammoniacal CuSO, while air is passed through. Other para diamins and naphthalene 
1.3-diamins can be used and sulfonation may take place after oxidation to azin. BLukr to VIOLET 
acid dyes. 

Note 603,013 and 606,295. 


1,015,354—Jan. 23, 1012. Otto Soust, Germany. (Hoéchst.) 
Trisulfonic acid of the safranin series and process of making same. 4’-Sulfo 

N-phenyl 4-sulfo benzyl ethyl 3-amino 4”’-ethoxy 6-imino phenazin. 

4’-Tolyl 4-PHENYLENE pIAMIN sulfo acid, homologs or derivs., and ethyl benzyl METANILIC 
acid, Na salt, in dil. Na,CO, soln., cooled to 5° and bichromate with HCl and acetic acid added, 
neut. with chalk and then boiled with suLFANILIc acid and more bichromate. Other sulfo acids 
of primary and tertiary amins with free para positions, are claimed. BuLiuer acid dyes for wool, 
that leave intermixed cotton fibers white. 


1,174,820—Mar. 7, 1916. - Rudolf Burcxuarpt, Switzerland. - (Durand.) 
Basic yellow-red dyestuffs of the safranin series and process of making 
same. N-Ethyl 6-ethyl tolazin. 


Nitroso ethyl 2-roLuripIn condensed with ethyl 3-ToLUYLENE DIAMIN by boiling in alc. HCl 
soln. Other components claimed. Orange-rEep direct or basic mordant dyes, suitable for printing. 


1,340,696—May 18, 1920. Andrea ANGEL, dec’d., England, by Mary L. ANGEL. 
Dyestuffs and process of making same. Parazin or benzenoid quinonoid dyes of new 
heterocyclic grouping of atoms. 


4-Chlor ANILIN, or 1.4-halogen amino naphthalene or anthracene comps. or derivs. heated 
at 200° with condensing agent such as ZnCl, FeCl,, AICl,, P,O;, etc., to a dihydro parazin 
which is oxidized to a parazin. Auxochrome groups can be introduced and special dyes produced. 
VARI-COLORED acid and basic dyes. 


GROUP VI.—AZO 67 


Group VI.—AZO. 


In the abstracts for Azo dyes the line giving the composition of the final 
product has been omitted, since this would be a repetition of the abstract itself. 

The word coupled is used as an abbreviation for diazotized and coupled. 

Combining weights are in the proportion of mol to mol, unless otherwise 
specified. 


204,799—June 11, 1878. Re. 9,144—April 6, 1880. Heinrich Caro, Germany. (Badische.) 
Dye-stuff or coloring-matter. 


NAPHTHYLAMIN coupled with 1- or 2-NAPHTHOL, then sulfonated or not, or either component 
may be sulfonated before coupling. Three methods of producing naphthylamin sulfo acids are 
given. Dark brown powds. strong organic acids, sol. conc. H,SO, (VB); rep acid dyes. 

S. ros—‘‘Sudan Brown” and S. 106, 111, 160-2, 166. 


210,054—June 10, 1878. F. X. Roussin, France. (Poirrier.) 
Improvement in coloring-matters derived from aniline and its homologs. 


SULFANILIC acid coupled with 1-NAPHTHOL, 2-napthol, resorcin, diphenylamin, or other 
phenol, amid, amin, or sulfo acid of same. RED, ORANGE, or YELLOW acid dyes. 
S. 136—‘‘Helianthin,” S. 139 “Orange IV,” 143, 144, 145, etc. : 


210,233—Nov. 26, 1878. Re. 9,986—Dec. 27, 1881. Heinrich Baum, Germany. (Hoéchst.) 
Coloring-matter or dye-stuff. : 


Xyiipin coupled with 2-naPHtTHOoL 3.6-disulfo. A red powd., easily sol. aq., sol. conc. 
H,SO, (YR), diff. sol. alc. (YR), gives usual azo separation when reduced with Sn and HCl; 
an orange RED acid dye. 

S. 82—‘‘Ponceau 2 R.”’ Note Re 9,987 for making and separating “‘R’’? from “G’’ salts. 


210,233—Nov. 26, 1878. Re. 9,987—Dec. 27, 1881. Heinrich Baum, Germany. (Hochst.) 
Coloring-matter or dye-stuff. 


XYLIDIN coupled with 2-NaAPHTHOL 6.8-disulfo, which acid is more soluble in alcohol and is 
thus separated from the insol. ‘‘R” salt. An orange red powd., freely sol. aq., sol. H,SO, (OR) 
and in HNO, (Y), diff. sol. alc. (OR), aq. soln., pptd. white by Br., sol. in excess; an orange 
RED acid dye. 


211,180—Jan. 7, 1879. 
Alcide F. Porrrier, Daniel A. RosENsSTIEHL, and Zacharie Rovussin, France. 
Improvement in colors from crude naphthylamine. 


PHTALAMIN and sulfo derivs. coupled with 2-NAPHTHOL, phenols, amins, and sulfo derivs. 
Phtalamin accompanies crude naphthylamin among the liquid products, its sulfo deriv. being 
more easily aq. sol. Dyes miy be further transformed by action of heat with aq. and alk. into 
different coloring matters. They are RED (orseille) acid dyes. 


211,525—Jan. 21, 1879. Zacharie Roussin and Alcide F. Porrrier, France. 
Improvement in colors derived from nitraniline. 


NITRANILIN*® and similar nitro naphthylamin, toluidin, or xylidin compounds coupled with 
NAPHTHIONIC acid, phenic acid, resorcin, phenylenediamin, 1- and 2-naphthols, amins, amids, 
phenols and sulfo comps. of same. YELLOW to RED acid or developed dyes, some sol. in aq., others 
insol. 

S. 52, etc.—‘‘Archil Substitute V.’’ *Obtained by action of alkalies on ‘‘nitrous acetanilid.” 


211,671—Jan. 28, 1879. Zacharie Roussin and Alcide F. Porrrisr, France. 
Improvment in colors derived from toluidine and xylidine. 

TOLUIDIN, XYLIDIN or sulfo deriv. coupled with 1-NAPHTHOL, 2-NAPHTHOL, DIPHENYLAMIN, OF 
other amin, amid, phenol or sulfo deriv. sulfonated before or after coupling. RED, ORANGE, or 
YELLOW acid dyes. byl 

S. zo—“‘Brill. Orange O,” and S. 76 “Sudan II,” etc. 


213,563—Mar. 25, 1870. John P. Grikss, England. (Badische.) 
Improvement in coloring-matters. 


ANIsipIn coupled with 1- or 2-NAPHTHOL disulfo (preferably beta). A red brown cryst. 
powd., sol. in aq. (R), and alc. (O), insol. in hydrocarbons, with alk. more yellow, with acids. 


68 DIGEST OF PATENTS 


more violet, sol. conc. H,SO, (V), decomp. on acid reduction into two amins; a RED acid or 
acid mordant. (Al) dye. 
S. 95—‘‘Azo-Cochineal.” 


213,564—Mar. 25, 1879. John P. Grisss, England. (Badische.) 
Improvement in coloring-matters. 

ANIsIDIN coupled with 2-NAPHTHOL sulfo, or other. A dark red cryst. powd., sol. in aq. and 
alc. (R), insol. hydrocarbon, soln. with alk. more yellow, with acid more violet, sol. conc. 
H,SO, (V), decomp. by acid reduction, giving anisidin, etc.; a RED acid or acid mordant (zinc 


aluminate) dye. 
Near S. 94—‘‘Azo Eosin G.” 


221,114—Oct. 28, 1879. James H. Sressins, Jr., New York. 
Improvement in colors from diazo-benzole nitrate and pyrogallol. 

Aniuin coupled with pyrocaLLoL in alk. soln. Dye is sol. in alc. and benzene, very readily 
sol. in acetic acid, insol. in aq. except as alk. or sulfo salt; a yellow BRowN direct or basic 


mordant (tannin) dye. 
“Pyrogallidine.” 


221,115—Oct. 28, 18709. James H. Sressins, Jr., New York. 
Improvement in colors from picric acid. 


ANILIN coupled with Picric acid in dil. alc. soln. Dark orange crysts., easily sol. alc. ether, 
and dil. HCl, as free acid is inso]l. in aqg.; an orange YELLOW direct or light YELLOW basic 
mordant (tannin) dye. 

“Picridine.”’ 


221,116—Oct. 28, 1870. James H. Sressins, Jr., New York. 


Improvement in coloring-matters obtained from diamido-naphthaline and 
diazo-naphthaline nitrate. 

NAPHTHALENE dinitrated in fuming HNO,, pptd. by diln., filt., dissolved in hot glacial 
acetic acid and cooled to separate the alpha dinitro product. This is reduced by Sn and HCl 
and freed from Sn by H,S, free diamino naphthalene being separated from soln. by heating with 
NaHCO,, which is coupled in alc. soln. with diazo naphthylamin nitrate. Browwn cryst. powd., 
upon recrystn. gives dark red star shaped crysts. easily sol. alc. and conc. H,SO, (deep B), 
slightly sol. aq.; BROWN acid and VIOLET (Sn) or BLACK (Fe) acid mordant dyes. 


221,117—Oct. 28, 1879. James H. Sressins, Jr.. New York. 
Improvement in coloring-matters obtained from cresol. 

ANILIN coupled with crEsoL in alk. soln., sulfonated before or after coupling. Brown 
crysts., easily sol. alc. (Y), insol. aq. as free acid, K salt sol. in boiling aq.; a YELLow direct 
Or ORANGE acid mordant (Sn) dye. 

“Cresolidine.” 


221,118—Oct. 28, 18709. James H. Sressins, Jr., New York. 
Improvement in coloring-matters obtained from salicylic acid. 
ANILIN coupled in alc. soln. with saticytic acid. Brown cryst. powd., easily sol. alc., 


sparingly sol. aq. as free acid, but sol. as Na salt or sulfo deriv.; an orange RED direct pale 
orange RED basic mordant or RED acid mordant (Sn) dye for silk or wool. 


221,119—Oct. 28, 1879. James H. Sresgins, Jr., New York. 
Improvement in coloring-matters obtained from naphthylamine and diazo- 
benzole nitrate. 
ANILIN coupled in alc. soln. with NAPHTHYLAMIN. Brown crysts., easily sol. cold alc., insol. 
in aq. as free acid, as K salt sparingly sol. aq., very sol. alc., easily sol. glac. acetic; a dark 


BROWN (silk), orange RED (cotton) or RED (wool) direct dye. 
‘‘Naphthylamidine.” 


221,120—Oct. 28, 1879. James H. Sressins, Jr., New York. 
Improvement in coloring-matters derived from toluol. 


ANILIN coupled in alc. soln. with TOLUYLENE DIAMIN. Orange cryst. powd., easily sol. 
boiling aq. or alc. (O), aq. soln. with HCl gives blood red crysts. of hydrochloride which are 


dine 


ae Sey J er 


ped. May O Luba. ee 


+s 


GROUP VI.—AZO 69 


sol. in aq. and alc.; an ORANGE acid dye or acid mordant (lead oleate or zinc aluminate) dye for 
cotton. 
S. 34—“Chrysoidin R.” 


224,927—Feb. 24, 1880. F. Kouuer, Germany. (Badische.) 
Dye-stufi or coloring-matter. 

Amino azo BENZENE mono sulfonated in 4 parts fuming H,SO, (twenty to twenty-five per 
cent SO,) at 60° then coupled with NaPpHTHOL disulfo in alk. soln. A brownish paste, sol. hot 
aq.; a RED acid dye. Called in patent ‘‘Fast Crimson, bluish shade.’’ 

Near S. 248—‘“Fast Scarlet B.” S. 247—‘‘Double Scarlet.” Schulz’ dye has two sulfo 
groups attached to the first component. Note 224,928. 


224,928—Feb. 24, 1880. F. Kouier, Germany. (Badische.) 
Dye-stuff or coloring-matter. 

Amino azo BENZENE sulfo coupled with 2-NAPHTHOL. A brownish paste, sol. in hot aq.; a 
RED acid dye, suitable for printing. 

S. 247—“‘Double Scarlet.”? Note 224,927 and S. 246, ‘‘Cloth Scarlet G’’ have one sulfo group 
and S. 247, two sulfo groups in first component, while above has none. Called ‘‘Fast Crimson’’ 
in patent. 


225,908—Mar. 23, 1880. F. X. Roussin, France. (Poirrier.) 
Artificial coloring-matter. (Process also claimed.) 
NAPHTHIONIC acid coupled with suLFANILIC acid, with other amins, amids, or phenols, their 


salts and sulfo acids except 1 or 2-naphthol and dioxy naphthalene (claimed in other patents), 
sulfonated before or after coupling. YELLOW to ORANGE to RED acid dyes. 


233,465—Oct. 19, 1880. H. Baum, Germany. (Hochst.) 
Red coloring-matter. 
Amino azo BENZENE coupled with 2-NAPHTHOL 3.6-disulfo acid in NH, soln. Product may 


be sulfonated. A RED acid dye, fast to washing and light. 
Near 227—“Brilliant Crocein M.” Note 210,233 for disulfo acid mfr. 


242,707—June 7, 1881. J. H. Srespins, Jr., New York. 
Azo color. 
ANILIN and NAPHTHYLAMIN mixture coupled 2-NAPHTHOL sulfo. Red brown crysts., 


easily sol. aq., sol. conc. H,SO, (V), aq. soln. with strong alk. KMnO, turns (YG), with Br aq. 
is decol.; a RED acid dye, fast to soap and light. 


246,221—Aug. 23, 1881. J. ScuuncKE, Bavaria. (Badische.) 
Azo color. 
Amino azo XYLENE coupled with 2-NAPHTHOL disulfo. in alk. soln. A black powd. of green 


metallic luster; a violet RED (archil or garnet) acid dye. 
S. 238—“‘Union Fast Claret.” 


246,272—Aug. 23, 1881. H. Baum, Germany. (Hochst.) 
Azo coloring-matter. 

Amino azo BENZENE sulfo coupled with 2-NAPHTHOL, sulfo (from 2-naphthol sulfonated in 3 
parts conc. H,SO,, at 25°), in alk. soln., preferably NH,. Product is freely sol. in aq. and dil. 
mineral acids, sol. conc. H,SO, (B), thus differing from 2-naphthol disulfo (V) or 2-naphthol 
deriv. (G), aq. soln. with alum gives no ppt.; a RED acid dye for wool and acid mordant (Al) 
dye for cotton. 


249,926—Nov. 22, 1881. J. H. O. Gurxr, Germany. (Hoéchst.) 
Coloring-matter. (Process also claimed.) 

4-Amino cINNAMIC acid, methyl ester, coupled with 2-NAPHTHOL 3.6-disulfo. <A dark red 
powd., easily sol. in aq. (R), conc. H,SO, (BR), in HNO, (YR), in dil. alk. (R), sparingly sol. 
alc. (pale R), aq. soln. pptd. by alc., color changed from red to yellow by Br.; a violet RED acid 
dye, fast to light and soap. 

Note 246,272. 


70 DIGEST OF PATENTS 


250,038—Nov. 22, 1881. H. Baum, Germany. (Hochst.) 
Manufacture of crimson coloring-matter. (Process also claimed.) 


Amino 4-cRESOL, methyl ether, coupled with 2-NAPHTHOL 3.6-disulfo in alk. (NH,) soln. 
Product is easily sol. in aq., sol. conc. H,SO, (dull RV), decomp. on acid reduction and cresol 
ether may be recovered; a deep violet RED acid dye, fast to light and soap. 

Note 246,272. 


251,162—Dec. 20, 1881. H. Baum, Germany. (Hochst.) 
Dye-stuff or coloring-matter. (Process also claimed.) 


ANILIN coupled with 2-NAPHTHOL 6.8-disulfo (made by sulfonation as described in 250,038, 
using the portion sol. in alc.). A powd. sol. in aq., and in conc. H,SO, (OR), decomp. on acid 
reduction; a yellow ORANGE acid dye, fast to light and soap. 

S. 38—‘Orange G’’ and S. 39—‘‘Ponceau G.’’ Note 251,163. 


251,163—Dec. 20, 1881. H. Baum, Germany. (Hochst.) 
Dye-stuff or coloring-matter. 


Ethyl xyxiipin coupled in alk. (NH,) soln. with 2-NAPHTHOL 3.6-disulfo derived from 2- 
NAPHTHOL heated with sulfuric acid, and two isomeric disulfo sodium salts separated by soln. in 
alc., using the insol. one. A powd. sol. in aq., sol. in conc. H,SO, (VR), decomp. on acid reduc- 
tion; a deep yellow rep acid dye, fast to light and soap. 

S. 83—“‘Ponceau R.’”’ Schulz gives pseudo cumidin as first component. . Note 251,163 and 
251,164, and for disulfo acid, 250,038. 


251,164—Dec. 20, 1881. H. Baum, Germany. (Hoéchst.) 
Dye-stuff or coloring-matter. (Process also claimed.) 


NAPHTHYLAMIN coupled with 2-NaPHTHOL disulfo (obtained as in 251,163 but using both 
disulfo acids). A powd. sol. in aq., sol. conc. H,SO, (G), differing thus from an) 799, decomp. 
by acid reduction; a violet RED acid dye, fast to Light and soap. 

S. 112—‘‘Fast Red B.” Note 204,799 and 251,163. 


253,598—Feb. 14, 1882. F. GRAESSLER, Germany. 
Manufacture of yellow coloring-matters. (Product, not process, claimed.) 


(a) Amino azo BENZENE, or salts, sulfonated in 3-5 parts fuming H,SO, (fifteen to twenty 
per cent SO,) at go-100° till'aq. sol. (may be mono, di, tri, or poly-sulfo) or (6) SULFANILIC 
acid (mono or disulfo) coupled with anitin. Products are sol. in aq. and alk.; yvELLow acid 
or acid mordant dyes, suitable for printing. 

S. 137—‘‘Fast Yellow.” S. 149—‘‘Fast Yellow Y.” No apparent difference between 
S. 137 and 149 is shown by Schulz, while patent in (a) and (b) indicates a difference. 


256,375—Apr. 11, 1882. C. Rumprr, Germany. 
Dye-stuff or coloring-matter. 


Amino azo TOLUENE sulfo coupled in alk. (NH,) soln. with 2-NaPHTHOL a-sulfo; a RED direct 
and acid dye. 
S. 255—‘‘Crocein Scarlet 8B.” Note 256,376 to 81, inc. 


256,376—Apr. 11, 1882. CC. Rumprr, Germany. 
Manufacture of dye-stuff or coloring-matter. (Product, not process, claimed.) 
I-NAPHTHYLAMIN sulfo coupled in ten per cent NH, soln. with 2-NAPHTHOL a-sulfo.; a RED 


acid dye. 
S. 167—“‘Crocein Scarlet 3BX.”’ Note 256,375. 


256,377—Apr. 11, 1882. C. Rumprr, Germany. 
Manufacture of dye-stuff or coloring-matter. (Product, not process, claimed.) 
2-NAPHTHYLAMIN sulfo coupled in ten per cent NH, soln. with 2-NaPHTHOL a-sulfo.; a RED 
acid dye. 
Note 256,375. 


256,37 8—Apr. 11, 1882. C. Rumprr, Germany. 
Manufacture of dye-stuff or coloring-matter. (Product, not process, claimed.) 
Amino azo XYLENE sulfo coupled in ten per cent NH, soln. with 2-NAPpHTHor, a-sulfo.; a RED 
acid and direct dye. 
S. 249—“‘Crocein Scarlet 3B.” Note 256,375. 


en Be ee 


ae eee 


a 


GROUP VI.—AZO is 


256,380—Apr. 11, 1882, C. Rumprr, Germany. 
Manufacture of dye-stuff or coloring-matter. (Product, not process, claimed.) 


Amino azo BENZENE sulfo coupled with 2-NAPHTHOL a-sulfo.; a RED acid, acid mordant (Al) 
or direct dye. 
Near S. 249—“‘Crocein Scarlet 3B.’”’ Note 256,375. 


256,401—Apr. 11, 1882. J. H. Sressins, Jr., New York. 
Dye-stuff or coloring-matter. 


NAPHTHYL sulfate prepared as in 256,400, coupled with diazotized amino azo BENZENE sulfo. 
Dye is easily sol. in aq. (R), less sol. alc. (R), sol. dil. oxalic acid (YR), insol. in ether, sol. in 
HNO, (B) and decomp. on heating, aq. soln. with lead acetate gives heavy red ppt., and with 
alum a slight red ppt.; a yellow-RED acid dye. 


257,242—May 2, 1882. C. Rumprr, Germany. 
Manufacture of brown dye-stuff. (Product, not process, claimed.) 


NaPHTHIONIC acid (mixture of sulfo acids formed by sulfonation of naphthylamin) diazo- 
tized in neutral or weak acid soln., preferably acetic, with sufficient NaNO, to diazotize oné 
half the amin. Product is sol. in aq., and is a BROWN acid dye, fast to soap and light and of 
good covering power. 

Note 257,243 for isomeric dye, 260,242 and 261,175 for other naphthylamin dyes. 


257,243—May 2, 1882. C. Rumprr, Germany. 
Manufacture of brown dye-stuff. (Product, not process, claimed.) 


2-NAPHTHYLAMIN sulfo, or other, diazotized in neutral or weak acid soln., preferably acetic. 
Products are sol. in aq., and are BROWN acid dyes, fast to soap, light and of good covering 
power. : 
Note 257,242. 


260,242—June 27, 1882. C. Rumprr, Germany. 
Manufacture of coloring-matter from naphthylamine. (Product, not process, 
claimed.) 


Amino azo BENZENE sulfo coupled with NAPHTHYLAMIN. A brown powd., sol. hot aq. and 
crysts. when cold, aq. soln. with alk. (YBr) and with acids (VR) and partly pptd.; a Brown acid 
dye. 

Note 257,242. 


261,175—July 18, 1882. C. RumprF, Germany. 
Manufacture of coloring-matter from naphthylamine. (Product, not process, 
claimed.) 


NaPHTHYLAMIN sulfo coupled with NAPHTHYLAMIN. A brown powd., sol. in hot aq. and 
cryst. when cold; aq. soln. (YB) with alk., (VR) with acids; a BRowN acid dye, fast to soap and 
light. 

Note 257,242. 


261,766—July 25, 1882. C. Rumprr, Germany. 
Manufacture of brown dye-stuff. (Product also claimed.) 

Amino azo XYLENE sulfo coupled with NAPHTHYLAMIN in acid soln. A dark brown powd., 
sol. in hot aq. soln., with alk. (Br), with acids (VR); a dark red BRowNn acid dye, fast to soap 
and light. 

Note 261,767 and 262,620. 


261,767—July 25, 1882. C. Rumprr, Germany. 
Manufacture of brown dye-stuff. (Product also claimed.) 


Amino azo TOLUENE sulfo coupled with NAPHTHYLAMIN. A brown powd., sol. hot aq., aq. 


soln. with alk. (Br), (VR) with acids; a dark red Brown acid dye, fast to soap and light. 
Note 261,766. 


262,620—Aug. 15, 1882. C. Rumprr, Germany. 
Manufacture of dye-stuff. (Product also claimed.) 
Amino azo BENZENE sulfo coupled with NAPHTHYLAMIN sulfo. A dark brown powd., sol. 
hot aq., with alk. (Br), with acids (VR); a dark red Brown acid dye, fast to soap and light. 
Note 261,766. P 


v2 DIGEST OF PATENTS 


268,113—Nov. 28, 1882. Re. 10,353—July 10, 1883. Carl Martius, Germany. 
Process of producing a basic coloring-matter from xylidine. 

XyLipIn HCl is heated to 280° in closed digester with METHYL alcohol to form “nitrate” of 
CUMIDIN, which is converted to base and fractionally distilled and cryst. to purify. (b.p. 235-236°, 
m.p. 62°). Product may be sulfonated. With 2-NAPHTHOL mono or disulfo acids product gives 
orange RED acid dyes. Claims aim to cover manufacture of cumidin, not derived dyes. 

Near S. 76 to 83. 


268,505—Dec. 5, 1882. C. F. L. Limpacu, Germany. (Hochst.) 
Manufacture of coloring-matter. (Product, not process, claimed.) 


Amino azo BENZENE sulfo coupled in NH, soln. with 2-NAPHTHOL trisulfo. Product is sol. 
in aq., in conc. H,SO, (BV), decol. by Sn and HCl; a violet rEp acid dye. 
Note 268,506 and 268,507, and Intermediates, same numbers. 


268,506—Dec. 5, 1882. C. F. L. Limpacu, Germany. (Hochst.) 
Manufacture of coloring-matter. 


I-NAPHTHYLAMIN sulfo coupled with 2-NAPHTHOL trisulfo. Product is sol. in conc. H,SO, 
(V, slowly changing to R), decomp. by Sn and HCl; a reEp acid dye. 
S. 170—‘Ponceau 6R.” Note 268,505 and 7. 


268,507—Dec. 5, 1882. C. F. L. Limpacu, Germany. (Hochst.) 
Manufacture of coloring-matter. (Product, not process, claimed.) 

Amino azo BENZENE coupled with 2-NAPHTHOL trisulfo. Product is sol. in conc. H,SO, (V, 
slowly changing to bluish), decomp. by Sn and HCl; a blue rep acid dye. 

S. 228—“‘Ponceau 5 R.” Note 268,505. 


269,359—Dec. 19, 1882. O. Wa.uacn, Germany. 
Manufacture of coloring-matter. (Product, not process, claimed.) 

ANILIN or other primary amin, coupled with REsorRcIN in alk. soln., and again coupled 
with diazotized suLFANILIC acid. Dark brown powds., easily sol. aq.; red BROWN acid dyes. 

S. 211—‘‘Resorcin Brown.” 


277,182—May 8, 1883. J. Wourr, Albany, N. Y. (Albany An.) 
Production of coloring-matters from diazoamido compounds. 
XYLIDIN, 1 mol., coupled with suLFANILIC acid or other, then with 2-NAPHTHOL disulfo in the 


same soln.; a yellow RED acid dye, possibly also direct dyeing. 
Patent is not clear as to composition. It may be a mixed mono azo dye. 


285,335—Sept. 18, 1883. J. Wourr, Albany, N, Y. (Albany An.) 
Manufacture of cardinal-red coloring-matter. (Product, not process, claimed.) 
NAPHTHYLAMIN coupled with sULFANILIC acid, then with 2-NAPHTHOL disulfo in the same 


soln., and 1 mol. NH, is added; a rEpD acid, possibly also direct dye. 
Patent is not clear as to whether a disazo or a mixed mono azo dye results. 


289,613—Dec. 4, 1883. O. Brept, Germany. 
Manufacture of red coloring-matter. (Product also claimed.) 

NAPHTHYLAMIN sulfo (mixed alpha and beta isomers), 3 mols., coupled with 1 mol. 2- 
NAPHTHOL by mixing in alk. soln. with nitrite, then making slightly acid with HCl; yELLow to 


violet RED acid dyes. 
*“‘Barmen Scarlets.” 


297,852—Apr. 29. 1884. Z. Rouissin and D. A. RosENsTIEHL, France. (St. Denis.) 
Manufacture of yellow and orange coloring-matters. 

4-Amino BENZOIC acid, isomers and homologs, coupled in alk. soln. with rEsorcin, diphenyl- 
amin, or other oxy or amino compounds. Dyes characterized by presence of COOH instead of 
SO,H; insol. aq. but alk. salts form dyes almost as soluble as sulfonic acids; YELLOW, ORANGE, or 
RED acid and mordant dyes. 

S. 203—‘‘Yellow, Soap fast.” 


GROUP VI.—AZO a3 


302,170—July 15, 1884. J. H. Sressins, New York. 
Manufacture of brown coloring-matter. 


Amino azo BENZENE 4-sulfo coupled in alk. soln. with 2-PHENANTHROL. A brown powd., sol. 
in aq. (BrR), in alc. (R), in acetone (R), conc. H,SO, (dull V), oxalic acid (RBr), slightly 
sol. HCl (Br), insol. in ether, decomp. by acid reduction; a BRown direct dye. 


302,790—July 29, 1884. Adolph Sprecet, Germany. (Hochst.) 
Azo coloring-matter. 


2-Amino dichlor PHENOL is coupled with 2-NAPHTHOL. Product which forms cryst. powd. 
(OR), is insol. in aq., with alk: (VB, sol. in alc.), as dry powd. or paste is refluxed at 100° in 
alc. soln. with two parts bisulfite until yellow crysts. of the bisulfite comp. form. Product is 
sol. in aq. (Y), decomp. by alk. or boiling nitrite and pptd. as sodium salt (BV); a rep acid 
dye for printing on cotton. 

S. 86—‘‘Azarin S.” 


303,335—Aug. 12, 1884. Adolph Sprrcet, Germany. (Hochst.) 
Azo coloring-matter. 


2-Amino dichlor PHENOL ccupled with ethyl 2-naPpHtTHoL then heated in alc. soln. with alk. 
bisulfite to form sol. bisulfite comp. Orange crysts., sol. in hot aq. (Y), soln. with alk. or 
nitrite is decomp., pptg. alk. salt (BV); a RED acid dye. 

Near S. 86—‘“‘Azarin S.”’ Addition to 302,790. 


306,969—Oct. 21, 1884. Adolphus Spircer, Germany. (Hochst.) 
Preparation of pheneto-sulpho-diazo-beta-naphthol with bisulphite com- 
pound. ; 


Dinitro DIPHENETOL sulfone reduced to diamino compound, coupled with 2 mols. 2-NAPHTHOL, 
then heated in alcohol with bisulphite. A pwd. or paste sol. in aq. (Y), decomp. by alk. or 
nitrite pptg. Na salt (O); an orANGE acid mordant dye, suitable for printing. 

Near S. 86—‘‘Azarin S$.” Note 302,790. 


309,882—Dec 30, 1884. Z. Roussin and A. A. RosrenstigHL, France. (St. Denis.) 
Manufacture of bromated azo coloring-matters. 
Orange I (SULFANILIC acid I-NAPHTHOL), 10 parts in dil. aq. soln. are mixed with 6 parts 


Br in dil. alk. and the whole made acid with 130 parts H,SO,, then pptd. as the Na salt. Other 
azo dyes may be similarly treated; yELLOW to ORANGE acid mordant dyes. 


310,155—Dec. 30, 1884. Leo Vicnon, France. 
Sulpho-alpha-naphthol coloring compound. 
I-NAPHTHOL mono sulfonated with H,SO, monohydrate below 25° or at 80° for a shorter 


time or in fuming H,SO, (twenty per cent SO,), and coupled with diazotized ANILIN in neut. or 
alk. soln.; an ORANGE acid dye. Other amins may be used. 


313,118—Mar. 3, 1885. James H. Sressins, Jr., New York. 
Red coloring-matter. 

Amino azo BENzOL sulfo coupled with diethyl ANILIN in methyl alcohol or HCl as solvent. 
Red-brown crysts. sparingly sol. in cold aq., freely sol. hot aq. (RBr), sol. conc. H,SO, (Br), 


in conc. HCl (deep B), becoming violet on diln. and pptg., aq. soln. with acids (V), with alk. 
color returns, decomp. by acid reducing agents; a brown RED acid dye. 


314,938—Mar. 31, 1885. Meinhard Horrmann, Germany. (Cassella.) 
Coloring-matter from beta-naphthol. 


Naputuionic acid coupled with 2-NAPHTHOL 6.8-disulfo in ammoniacal soln. by slowly adding 
the diazo soln. to the alk. coupling soln.; a violet RED acid dye. 
S. 169—‘‘Cochineal Red A.” Note 314,939. 


814,939—Mar. 31, 1885. Meinhard HorrmMann, Germany. (Cassella.) 

Red coloring-matter from gamma disulphonic acid of beta-naphthol. 
Amino azo BENZENE coupled with 2-NAPHTHOL 6.8-disulfo in dil. NH, soln. <A red pwd., 

giving green crysts. upon recrystn., sol. conc. H,SO, (V), aq. soln. pptd. by acid; an orange RED 


acid or acid mordant dye. 
S. 227—“Brilliant Crocein M.” 


74 DIGEST OF PATENTS 


829,632—Nov. 3, 1885. Carl Duissperc, Germany. 
Coloring-matter obtained from tetrazo-ditolyl. 


ToLIDIN tetrazotized and coupled in acetic acid soln. with 2 mols. NAPHTHIONIC acid. A 
brown-red powd., diff. sol. hot aq., soln. with acids (B), unchanged by alk.; a rEp direct dye 
less sensitive to acids and light than Bottiger’s dye from benzidin and naphthionic acid. 

S. 363—‘‘Benzopurpurin.” Note 329,633. 


329,633—Nov. 3, 1885. Carl Duisperc, Germany. 
Coloring-matter obtained from tetrazo-ditolyl. 


ToLipIN tetrazotized and coupled in acetic acid soln. with 2 mols. 2-NAPHTHYLAMIN sulfo. 
A red pwd., easily sol. hot aq., sepd. by conc. acids as free dyestuff acid, isomeric with 329,632; 
a RED direct dye, yellower than alizarin but faster to acids and light. 

S. 365—‘“‘Benzopurpurin B.” 


329,634—Nov. 3, 1885. Emil E.sagsser, Germany. 
Red dye-stuff or coloring-matter. 


2-NAPHTHYLAMIN 5-sulfo (‘“‘Dahl’s’”? acid) coupled with 1-NAPHTHOL 4-sulfo or other mono 
sulfo acid of 1-naphthol. Red brown pwd., easily sol. hot aq., sol. conc. H,SO, (R), decomp. 
by reduction with Zn dust (B), with HCl ppts. free naphthylamin sulfo acid; an ORANGE 
to violet RED acid dye. 


329,638—Nov. 3, 1885. Eugen Frank, Germany. (Bayer.) 
Yellow coloring-matter. 


BENzIDIN sulfate coupled in alk. soln with 2 mols saLicyLic acid, or other oxybenzoic acid. 
A brown red pwd., or a paste, diff. sol. hot aq., depositing yellow cryst. needles on cooling, aq. 
soln. with acids turns (VR), with alk. (Br); a yELLow direct dye, ‘fast to scouring and light. 
S. 342—“Chrysamin G,” S. 394—‘“‘Chrysamin R.” 


329,639—Nov. 3, 1885. Eugen Frank, Germany. 
Production of new yellow coloring-matter. 


BENZIDIN sulfo coupled in alk. soln. with 2 mols. saticyziic acid or other oxybenzoic acid. 
A brown red pwd. or paste, diff. sol. hot aq., on cooling form needles (Y), aq. soln. with acids 
(VR) with alk. (Br); a yELLow direct dye fast to scouring and light. 

S. 342—‘“‘Chrysamin G.”? Note 329,638. 


332,528—Dec. 15, 1885. Meinhard HorrmMann, Germany. (Cassella.) 
Dye-stuff made from diazo-naphthaline. 


I-NAPHTHYLAMIN coupled in alk. carb. soln. with 2-NAPHTHOL 6.8-disulfo. A red pwd. or 
crysts., easily sol. hot aq., sol. conc. H,SO, (B), not pptd. on diln.; a violet rED acid dye, 
capable of dyeing violet BLUE, and readily crystallizable. 

S. 113—‘“‘Crystal Ponceau.” Note 314,938. 


332,829—Dec. 22, 1885. Hugo Prinz, Germany. (Broénner.) 
Manufacture of beta-naphthylamine sulpho-acid. 


2-NAPHTHYLAMIN 6-sulfo coupled with 1-NAPHTHOL. N. B. Patent actually claims only the 
intermediate, not derived dyes. (See Schulz). A BROowN acid dye. 
S. 172—“‘Fast Brown 3 B.’’ Note 174, 176. 


332,830—Dec. 22, 1885. Hugo Prinz, Germany. (Broénner.) 
Red coloring-matter from betanaphthylamine sulpho-acid. (Process also 
claimed.) : 


2-NAPHTHYLAMIN sulfo coupled with 2-NAPHTHOL disulfo (mixed isomers). Product is sol. 
in conc. H,SO, (YR) while Caro’s dye Re. 9,144 gives a violet and Baum’s 251,164 a green color, 
gives usual azo reduction with Sn. and HCl; a rep acid dye. 

For mfr. of sulfo acid, see 332,839. 


333,035—Dec. 22, 1885. H. Vouiisrecut and C. Menscuinc, New York. (Schoellkopf.) 
Coloring-matter derived from alphanaphtholdisulphonie acid. 

XyYLIpDIN coupled with 1-NAPHTHOL 4.8-disulfo in presence of excess alk. for neutn; a RED 
acid dye. When nitrated, 1-naphthol 4.8 disulfo forms 1-naphthol 2.4-dinitro 8-sulfo acid, a 
YELLOW acid dye. 

S. 80—‘‘Wool Scarlet R’ and S. 5 (1902)—‘“Brill. Yellow S.’? Note this patent and 
333,034 for mfr. of “S” acid. 


Seta aa ate 


GROUP VI.—AZO 75 


333,037—Dec. 22, 1885. H. Voiisrecut and C. Menscuinc, New York. (Schoellkopf.) 
Manufacture of dye-stuff from naphthol. 

Amino azo BENZENE coupled with 1-NAPHTHOL 4.8-disulfo; a RED direct dye. 

S. 226—“Crocein B.” Note 333,034, 5, 6, 7, 8, and 9, for mfr. of sulfo acid. 


333,038—Dec. 22, 1885. H. Voirsrecut and C. Menscuinc, New York. (Schoellkopf.) 
Manufacture of dye-stuff from naphthol. 


TOLUIDIN coupled with 1-NAPHTHOL, 4.8-disulfo; a rED acid dye. 
Note 333,034 to 9 iné., etc. 


333,039—Dec. 22, 1885. H. Voitiprecut and C. Menscuinc, New York. (Schoellkopf.) 
Coloring-mater derived from diazohenzol and alphanaphtholdisalphonle 
acid. 


ANILIN coupled with 1-NAPHTHOL 4.8-disulfo. A yELLOow acid dye. Original patent for sulfo 
acid ‘‘S” is Intermediate 333,034. 


333,041—Dec. 22, 1885. H. Voiitprecut and C. Menscuinc, New York. (Schoellkopf.) 
Coloring-matter derived from diazobenzol and alphanaphthol. 


I-NAPHTHOL 5-Sulfo formed as in 333,040 from sol. portion of mixed naphthylamin sulfo 
acids, coupled with diazo ANILIN or SULFANILIC acid. Orange RED acid dyes. 


333,042—Dec. 22, 1885. H. Voiiprecut and C. Mrenscuinc, New York. (Schoellkopf.) 
Coloring-matter derived from alphanaphthol and diazotoluol. 


ToLuIpIN sulfo, or other, coupled with 1-NAPHTHOL 5-sulfo formed as in 333,034 from 
soluble portion of mixed sodium salts of naphthylamin sulfo acids. ORANGE to violet RED acid 
dyes. 

Addition to 333,041. 


334,25 7—Jan. 12, 1886. C. Alexander Martius, Germany. (Brénner.) 
Manufacture of archil-red azo colors. 


4-NITRANILIN coupled in acetic acid soln. with 2-NAPHTHYLAMIN 6-sulfo; violet RED acid dye. 


341,991—May 18, 1886. F. BenpEr, Germany. (Leonhardt.) 
Production of yeliow azo coloring-matter. (Product also claimed.) 

3-NITRANILIN or sulfo deriv., coupled in acid soln. with 3-PHENYLENE DIAMIN. A brown 
red powd. or needles, m.p. 204°, diff. sol. hot aq., sol. in ale. (OY), hot aq. soln. with acid 
forms red gel., large amt. of aq. dissociates dye, and free bases cryst., NH, helps latter pptn., 
easily sol. fuming H,SO, and HNO, (Y), reduced by Zn or SnCl, and HCl, reduced liquid with 
FeCl, gives unstable red color; YELLOW to BRowN basic dyes. 


342,432—May 25, 1886. C. Duisperc, Germany. 
Blue coloring-matter from nitrophenetol. (Process also claimed.) 
DIPHENETIDIN (by alk. reduction of NITROPHENETOL and transforming the resulting hydrazo 


comp. by conc. acids), coupled in organic acid soln. with two mols. 2-NAPHTHYLAMIN sulfo; 
a violet RED direct dye. 


344,075—June 22, 1886. F. Benper, Germany. (Leonhardt.) 
Production of yellow coloring-matter. 


as-nitro amino BENzOoIC (by reduction of dinitro benzoic), coupled with 3-PHENYLENE DIAMIN. 
A brown powd., easily sol. hot aq., forms salts with bases and acids, the latter only being 
dyes, hot soln. not pptd. by acids, slight pptn. with acetic acid, reduced by Zn and HCI, filtrate 
from reduction is unstable red color; a YELLOW basic dye. 


344,971—July 6, 1886. C. A. Martius, Germany. 
Producing mixed azo colors. (Product, not process, claimed.) 


BENZzIDIN or TOLIDIN, coupled with naPpHTHIoNIC acid, or other aromatic amino comp., 
then with 2-NAPHTHYLAMIN sulfo, or other aromatic amin or phenol or their sulfo acids. RED 
to vIoLET direct dyes. 

S. 312—“‘Congo Corinth G.” Note 358,865. 

6 


76 DIGEST OF PATENTS 


345,901—July 20, 1886. M. HorrmMann and A. WEINBERG, Germany. (Cassella.) 
Naphthol-black color compound. 


Process and claims the same as in Re. 11,598, which follows, except the wording of patent 
is more accurate in the latter. 


345,901—July 20, 1896. Re. 11,598—April 27, 1897. 
M. HorrMann and A. WEINBERG, Germany. (Matheson.) 
Naphthol-black color compound. 


NAPHTHYLAMIN disulfo coupled in acid soln. with 1-NAPHTHYLAMIN, again diazotized and 
coupled in alk. soln. with 2-NAPHTHOL 3.6-disulfo. A black powd. or paste, easily sol. aq., 
insol. in alc., sol. conc. H,SO, (G), decomp. on reduction; a dark siux acid dye. 

S. 269>—‘“Naphthol Black 6B” and S. 272—‘‘Naphthol Black B.” 


354,746—Dec. 21, 1886. L. Scuap, Germany. 
Production of coloring-matter. 


Amino azo BENZENE disulfo, coupled with 4-tolyl 2-NAPHTHYLAMIN. A blue BLAcK direct dye. 
The working of patent is so obscure that it is difficult to determine whether a mono or 
disazo dye is described. ‘The color indicates disazo. 


356,672—Jan. 25, 1887. H. Voiisrecut and C. Menscuince, New York. (Schoellkopf.) 
Red coloring-matter from alpha diazo beta-naphthylamine sulphonie acid. 


I-NAPHTHYLAMIN 5-Sulfo coupled with 2-NAPpHTHOL in alk. soln. A Rep acid dye, more 
yellowish shade than “Rocelline” which is made from Piria’s naphthionic acid. Rocelline is 
sol. in conc. H,SO, (B), while new dye is (RV). 

“Brilliant Red.” 


357,273—Feb. 8, 1887. C. Duisserc, Germany. 
Blue coloring-matter from tetrazodiphenyl. (Process also claimed.) 


DIANISIDIN (by reduction of NITRANISOL and treatment with conc. acid) coupled with 2 
mols. 1-NAPHTHOL 4-sulfo. A black powd. with bronze hue, easily sol. aq. (VB), sol. in 
alk. (R), sol. conc. H,SO, (deep B); a deep siue direct dye, fast to warm soap and mineral 
acids. 


S. 411—‘“‘Benzo Azurin 3G.” Note 213,563-4, 481,054, and 357,274. 


357,274—Feb. 8, 1887. C. Duiszerc, Germany. 


Red coloring-matter for dyeing by the action of tetrazo dyes with beta- 
naphthylamine sulpho acid. (Process also claimed.) 


DIANISIDIN, coupled in organic acid soln. with 2 mols. 2-NAPHTHYLAMIN sulfo. A red powd., 
easily sol. hot aq., insol. in alc., sol, conc. H,SO, (B), decomp. on reduction; a deep BLUE 
(strong acid bath) to violet RED (alk. bath of phosphate or carbonate) direct dye, fast to dil. 
acids and alk. 


Near S. 405—‘‘Benzopurpurin, 10B.” Isomer of Benzopurpurin, which is the 1-naph- 
thylamin sulfo product. 


358,865—Mar. 8, 1887. C. A. Martius, Germany. 
Production of mixed azo coloring-matter. 

BENZIDIN, TOLIDIN, or other diamin, coupled with 1-NAPutHoL sulfo, then with 1I-NAPH- 
THYLAMIN sulfo. The second coupling agent may or may not be the same as the first, a long 
list of different components being given in six classes. VARI-cOLORED direct dyes. 

S. 312—‘‘Congo Corinth S$.” Note 344,971. 


359,57 6—Mar. 15, 1887. A. Romer, Germany. (Badische.) 
Manufacture of red coloring-matter. 

I-NAPHTHALENE DIAMIN diazotized in presence of large excess HCl, coupled with 2 mols. 
NAPHTHIONIC acid in organic acid soln. Tests for end of reaction and for diamin in reduced 
dye to distinguish same from benzidin, etc., are given. Dye soln. with conc. HCl ppts. (dull 
YG), while Congo Red and Benzopurpurin ppt. (B); decomp. by Zn dust, amin extracted in 
CS, and Br added gives (RT), while other two dyes are (intense B); a rep direct dye. 

Near S. 432—‘‘Diamin Catechu.” 


ae 


Re ee ee ee etre. ee 


GROUP VI.—AZO 77 


360,792—Apr. 5, 1887. F. Benper and G Scuuitz, Germany. (Leonhardt.) 
Obtaining diazo colors by means of diamido-stilbene and diamido-fluorene. 


Diamino STILBENE or diamino FLUORENE tetrazotized and coupled with 2 mols. of an amin, 
a phenol, their sulfonates or carbonates, or with two different mols. of an amin or phenol, 
etc. Lists of these are given. VARI-coLORED direct dyes. 


361,404—Apr. 19, 1887. Paul FrrepLAENDER, Germany. (Oehler). 
Combination of tetrazodiphenyl chlorire with resorein. (Process and product 
claimed.) 


BENZIDIN, tolidin, etc., coupled with 2 mols. RESoRcINoL in alk. carb. soln. A red brown 
cryst. pwd., diff. sol. aq. (BrR), aq. soln. turns red with NaOH and is pptd. (Br) by acids; 
a direct RED dye. 

S. 317—‘“Pyramidol Brown BG.” Schulz states that by coupling with diazo solns. a 
brown color is produced. 


3862,813—May 10, 1887. Friedrich Bayrer, Germany. (Bayer.) 
Yellow-red dye-stuff from tetrazo-diphenyl. (Product.) 

BenzipIn coupled in organic acid soln. with 2-NAPHTHYLAMIN 7-sulfo (Bayer’s or d-acid). 
A red pwd, easily sol. hot aq., soln. not changed by acetic acid, pptd. by HCl (Br), sol. conc. 
H,SO, (B); an orange rep direct dye. 

Note 363,502. 


363,502—May 24, 1887. Friedrich Bayer, Germany. (Bayer.) 
Manufacture of dye-stuffs and coloring-matter. 


ToLIDIN coupled in organic acid soln. with 2 mols, 2-NAPHTHYLAMIN 7-sulfo (delta acid.) 
A brown red pwd. easily sol. in aq., sol. with HCl ppts. free dye acid (Br), sol. conc. H,SO, 
(B); a violet rEp direct dye, fast to acetic acid. 

S. 367—‘“Diamin Red 3 B.’’ Schulz credits this dye to Weinberg, 1886. Note 362,813. 


365,409—June 26, 1887. Joseph Rouner, Switzerland. (Basle.) 
Production of new coloring-matter. (Product, not process, claimed.) 


Amino AZO BENZENE or other amino azo comp., coupled with 3-TOLUYILENE DIAMIN or 3- 
PHENYLENE DIAMIN. Products are diff. sol. aq.; BROWN to brown vIOoLET direct dyes. 


365,666—June 28, 1887. Paul Borrricrer, Russia. (Berlin.) 
Manufacture of new red dye-stuffs or coloring-matters. 

Benzipin coupled with 2 mols. 1- or 2-NAPHTHYLAMIN or their sulfo acids, or mixtures 
thereof. Dye may be mono- or di-sulfonated after coupling, with conc. H,SO,, the anhydride, or 
monochlorhydrin. Rep direct dyes. 


365,667—June 28, 1887. Paul Borricer, Germany. (Berlin.) 
Combination of the salts of tetrazo-diphenyl and the naphthylamines,. 
BENz1pIN coupled with 2 mols. 1- or 2-NAPHTHYLAMIN, NAPHTHIONIC acid or other sulfo 


acids. Rep direct dyes. 
S. 307—“‘Congo Red.” Note 365,666 for process. 


366,078—July 5, 1887. Carl Duisserc, Germany. (Bayer.) 
Manufacture of dye-stuffs or coloring-matters. 


2- or 4-TOLIDIN coupled with 2 mols. 1-NAPHTHOL 4-sulfo. A black pwd., easily sol. hot 
aq., (RV), conc. soln. pptd. by mineral acids (RV), diff. sol. alc. and glac, acetic (VR), insol. 
conc. NaOH, easily sol. dil. NaOH or twenty per cent NH, (R), Sol. conc. H,SO, (B); a 
violet BLUE direct dye (alk. bath with silicate or phosphate of Na), fast to mineral acids. 

S$. 377—“‘Azo Blue.” 


375,848—Jan. 3, 1888. A. WEINBERG and H. Sigepert, Germany. (Cassella.) 
Manufacture of dye-stufis. 

TouipIn coupled with 2 mols. I1-NAPHTHYLAMIN sulfo in presence of excess Na acetate or 
carbonate. A red pwd., easily sol. in aq., sol. conc. H,SO, (B) turning brown on diln; a rp 
direct dye, fast to alk. and weak acids, and of good covering power. 

S. 367—“‘Diamin Red 3B.” Dye is isomeric with 329,635 (Duisberg). 


78 DIGEST OF PATENTS 


375,930—Jan. 3, 1888. P. FRIEDLAENDER and B. Priress, Germany. (Oehbler.) 
Production of orange azo dye-stuffts. (Product also claimed.) 

ToLipIN coupled with 1 mol. each of 3-TOLUYLENE DIAMIN sulfo and gsaLicyLic acid in alk. 
soln. A red brown pwd., easily sol. hot aq. (O), insol. in hydrocarbons, soln. pptd. by acids 


(BrR), sol. conc. H,SO, (V); an orANGE direct dye, fast to soap and dil. mineral acids. 
Near S. 592—‘‘Toluylene Orange G.”’ 


376,392—Jan. 10, 1888. Adelbert Myutins, Switzerland. (Geigy.) 
Production of a new red azo color. 


4-NITRANILIN coupled with 1-NAPHTHYLAMIN 4.7- or 4.6-disulfo; a RED acid dye. 
S. 54—‘‘Apollo Red B.” 


380,067—Mar. 27, 1888. A. WEINBERG, Germany. (Cassella.) 
Production of new diamid compounds and of azo colors produced therefrom. 
2-Ethoxy BENZIDIN, or other ethers of oxy diphenyl comps., coupled with 2 mols. SALICYLIC 
acid, or 1 mol. each of two amins, phenols, or sulfo or carboxyl derivs. thereof. YELLOW, RED, 
BLUE Or VIOLET direct dyes. 
S. 401—‘“‘Diamin Blue 3R.” S. 404—‘‘Diamin Yellow N.” 


380,098—Mar. 27, 1888. T. DieHL, Germany. (Zimmer.) 

Coloring-matter from the sulpho-acids of ethyl or diphenylamine combined 
with tetradiphenyl or tetrazoditolyl. (Process, not product, claitned.) 
BENZIDIN, TOLIDIN, or similar comp., coupled with 2 mols. ethyl ANn1ILIN sulfo or other sulfo 

acids of ethyl anilin or diphenylamin, in acetic soln. or with 1 mol. above and 1 of an amin, 


phenol, salicylic acid, phenol or naphthol or naphthylamin sulfo acid. YELLOW to RED to VIOLET 
direct dyes, of fiery tint and fast. 


380,402—Apr. 3, 1888. L. Paut, Germany. 
Production of disuipho and dicarbo acids of the diamidoazo-benzidines. 
(Product claimed.) 
3.3’-Diamino DIPHENYL 4.4/-dicarbo acids, coupled with 2 mols. 1- or 2-NAPHTHYLAMIN, OF 
with 1 mol. each of two coupling agents, again tetrazotized and coupled with 2 mols. 2-NAPHTHOL 
3-6-disulfo, or other. Or tetrazo comp. coupled with one mol. coupling agent, then boiled in 
dil. acid to give hydroxyl comp. Very long and complex claims. Vari-coLorEp direct dyes. 


380,403—Apr. 3, 1888. L. Paut, Germany. 

Production of disulpho and dicarbo acids of the diamidoazo-benzidines. 
BENZIDIN, TOLIDIN, or diamino dixylyl, coupled in organic acid alc. soln. with METANILIC 

acid, then in alc. alk. carb. soln. with another mol. of same. Other anilin sulfo acids, amino 


benzoic acids, toluidin or xylidin sulfo acids as second components are claimed. YELLOW, RED 
to BROWN direct dyes. 


Note 358,865 (Martius) for same components combined in aq. soln., which yields mono 


azo only. Patent claims different product in alk. soln. giving reason and tests, “not a disazo 
compound.” 


380,927—Apr. 10, 1888. A. F. Porrrier and D. A. RosEenstTigHL, France. (Soc. Chim.) 
Production of azo colors. (Product claimed.) . 

3-NITRANILIN, 3- OF 4-nitro toluidin (m.p. 107° and 78°), nitro-xylidin, (m.p. 123°), or other 
nitro aromatic amin, reduced in dil. NaOH with Zn powd. at a boil, separated, tetrazotized, 
and coupled with 2 mols. 1-NAPHTHOL 5-sulfo ‘‘Piria’ or other phenol, oxyphenol, naphthol, 
oxynaphthol, primary, secondary or tertiary amins diamins, and alkyl., sulfo and carboxyl 
derivs. of these. Long list given. Soluble vari-coLorEp direct and acid mordant dyes. 


380,92S—Apr. 10, 1888. A. F. Porrrrer and Z. Roussin, France. (St. Denis.) 
Production of diazoic coloring matters. (Product claimed.) 

4-NITRANILIN, nitro toluidin, or nitro xylidin, coupled with Witts (Ber. 79, 578) 1-NAPHTHY- 
LAMIN sulfo in acid soln., or with other isomer of naphthionic acid. YELLOW, RED, to BROWN acid 
dyes. 

S. 55—‘‘Archil Substitute 3VN.” 


Se ee a ee ae 


GROUP VI.—AzO 79 


381,045—Apr. to, 1888. O. N. Wirt, Germany. (Badische.) 
Manufacture of purple-black azo dye-stuff. (Product, not process, claimed.) 
@S-DINITRANILIN (Gottlieb), coupled with 2-NAPHTHYLAMIN sulfo, (Brénner) in acetic acid 
soln., or with delta sulfo acid, but not other isomer. <A. black powd., easily sol. boiling aq. 
(deep V), and on cooling, if pure, remains liquid, but if slightly alk. forms BrR gel. that 
liquefies on heating; a vioLet acid dye. 
Note 381,046. 


381,046—Apr. 10, 1888. O. N. Wirt, Germany. (Badische.) 
Purple azo dye-stuff. 

@S-DINITRANILIN (Gottlieb), m.p. 180°, coupled in acetic soln. with 2-NAPHTHYLAMIN  3.6- 
disulfo (derived from “R” acid by heating with NH, under pressure). A jet black powd., 
easily sol. cold aq., unchanged by alk., pptd. by excess, with acids (deep R), sol. conc. H,SO, 
(R); a vIoLET acid dye. 

Note 381,045. 


881,1832—Apr. 17, 1888. FE. HassENKAMP, Germany. (Dickerson.) 
Production of blue-red azo dye-stuff by the action of tetrazo-ditolyl salts 

on betanaphthylamin monosulpho acid. 

ToLiIpIn coupled in acetic soln. with 2 mols. ethyl 2-NAPHTHYLAMIN 5-sulfo in acid soln. 
A brown red powd., easily sol. aq., sol. conc. H,SO, (B); a violet rep direct dye. 

S. 372—“‘Rosazurin B.” Note 381,471. 


381,471—Apr. 17, 1888. E. Hass—EnKAmp, Germany. (Dickerson.) 
Process of producing blue-red coloring-matter. 

BENzIDIN or other para diamin, or their sulfo or carboxylic acids, coupled with 2 mols. 
methyl 1-NAPHTHYLAMIN sulfo, (derived from 1-naphthylamin sulfo by alkylating with methyl 
sulfo acid in autoclave at 180-200°), or other alkyl naphthylamin sulfo acid. Product is 
easily sol. aq., sol. conc. H,SO, (B); a violet rEp direct dye, fast to dil. acids. 

Note 381,132. 


384,315—June 12, 1888. M. Herzserc, Germany. (Bayer.) 
Manufacture of dye-stuffts. 

BENZIDIN, or other aromatic amino, diamino, amino azo or nitro sulfo or carbo acid derivs. 
thereof, coupled with 1-2 mols., tetra amino disazo BENZENE (Bismarck Brown). Products are 
then sulfonated to render aq. sol. Brown direct dyes. 

S. 485—‘“‘Benzo Brown G.” Note 384,316. 


384,316—June 12, 1888. M. Herzserc, Germany. (Bayer.) 
Manufacture of dye-stuffs. (Product, not process, claimed.) 

NapPuTuHionic acid coupled with tetra amino disazo BENZENE, or toluene (Bismarck Brown). 
The claims of this patent are identical with example II in 384,315 patent. A brown powd., 
easily sol. aq., soln. with HCl ppts. free dye acid, sol. conc. H,SO, (VBr); a Brown direct 
or acid dye. 


384,342—June 12, 1888. R. G. Wiitiams, New York. 
New coloring-matter obtained by the action of tetrazo-diamino benzole on 
phenols. 


PHENYLENE DIAMIN, or homologs, coupled in acetic acid soln. with 2 mols. RESORCIN, or other 
phenol, amin, amid, or their substitution prods. Products are sol. in alk., insol. dil. acids; 
BROWN direct dyes. 


386,192—July 17, 1888. S. Foret, Germany. 
Obtaining oxyazoic coloring-matter from tetrazo diphenyl and ditolyl. 


(Product also claimed.) 
BENZIDIN, or TOLIDIN, coupled in alk. soln. with 2 mols. 2-cRESOL, or PHENOL. YELLOW direct 
dyes fast to soap, acids, and light. 


So DIGEST OF PATENTS 


388,185—Aug. 21, 1888. C. Duisperc, Germany. 
Blue azo coloring-matter. 

DIPHENETIDIN, coupled with 2 mols. 1-NaPHTHOL 4-sulfo. A black amorph. powd. with 
bronze hue, sol. in aq. (V), with alk. (R), sol. conc. H,SO, (B); a sive direct dye, fast to soap 
and mineral acids. 

S. 411—“‘Benzoazurin 3G.” Note 357,273. 


389,127—Sept. 4, 1888. H. Wo.urr, Switzerland. 
Production of new azo colors. (Product also claimed.) 
3-Nitro diamino TRIPHENYLMETHANE, or sulfo derivs., coupled in alk. soln. with 2 mols. 2- 


NAPHTHOL or other aromatic phenol, naphthol, amino or diamino comp. or their sulfo derivs. 
Orange RED direct dyes. 


394,425—Dec. 11, 1888. R. G. WiiiiAMs, New York. 
Action of salts of tetrazo-ditolyl or diphenyl on dihydroxides of toluene or 
their sulpho-acids. (Product, not process, claimed.) 


BENZIDIN, TOLIDIN, or their sulfo derivs., coupled with 2 mols. orcrn or other deriv. of 
toluene and sulfo acids of same. Products are insol. in dil. acids, sol. conc. H,SO, (V); and are 
RED direct dyes, fast to soaping. 

Note 404,331. 


394,841—Dec. 18, 1888. C. Dutsperc, Germany. (Bayer.) 
Manufacture of coloring-matters. 

BENZIDIN, tolidin, or diphenetidin coupled with 2 mols. cresol carboxylic or ‘‘cRESOTINIC” 
acid. A brown red powd. somewhat sol. hot aq., easily sol. boiling soap (Y), soln. with alk. 
(RBr), with acid decol. and pptd., sol. conc. H,SO, (V); an orange RED direct dye fast to 
scouring and light. 

S. 351—‘“‘Cresotin Yellow G.” Patent calls this a yellow dye but says a yellow red color 
is produced on cotton. Schulz reports a yellow color on cotton. 


395,474—Jan. 1, 18809. F. Bayer, Germany. (Bayer.) 
Manufacture of dyestufis or ccloring-matters. 


BEnzIpIN tolidin, diphenetidin, diamino stilbene, or their sulfo acids, coupled with 2 mols. 
2-NAPHTHYLAMIN 7-Sulfo or ‘“‘delta’’ acid (see Intermediates). Rep direct dyes. 


395,634—Jan. 1, 1880. C. RupotpH and B. Prigzss, Germany. (Oecehler.) 
Orange azo dyestuff. 

ToLipIN coupled in alk. carb. soln. with 1 mol. each of 2- or 3-CRESOTINIC acid and 3- 
TOLUYLENE DIAMIN sulfo. A red brown pwd., easily sol. hot aq., sol. conc. H,SO, (VR). 


ORANGE direct dyes. 
S. 392—‘‘Toluylene Orange G.”’ 


396,293—Jan. 15, 1880. Christian RupotpH, Germany. (Oehler.) 


Tetrazo dyestuff. 


2-, 3-, or 4-Amino crEsoL sulfo acid coupled with 1-NAPHTHYLAMIN, sepd., washed, dissolved 
in NH,, rediazotized and coupled with 2-NAPHTHOL 3.6-disulfo. A black brown pwd., with 
bronze luster, sol. in aq. (BV), soln. with NH, pure blue, sol. conc. H,SO, (G); a violet 
BLUE to blue BLACK direct dye. 5 


396,294—Jan. 15, 1880. C. RupotpH and B. Prirgs, Germany. (Oehler.) 


Yellow coloring-matter. 

BENZIDIN, or tolidin, coupled with 2- or 3-cRESOTINIC acid then with saLicyLic acid. A 
brown yellow pwd., easily sol. hot aq., sol. conc. H,SO, (VR). YELLow direct dyes. 

Near S. 361—‘“‘Cresotin Yellow G.’? Note 329,638 (Frank), 394,841, and 395,634. 


398,990—Mar. 5, 1880. Johannes WALTER, Switzerland. (Geigy.) 
Process of making a yellow dye. 


Thio 4-ToLUIDIN sulfo coupled with saticyLic acid in alk. soln. A YELLOW direct dye, fast 


to light and Cl, suitable for printing. 
S. 195—‘‘Rosephenine SG,” S. 197—‘‘Thiazin Red G,” and S. 199—“Oriol Yellow.” 


GROUP VI.—AZO SI 


399,581—Mar. 12, 1880. Josef SrrasBuRGER, Russia. (Berlin.) 
Process of making a brown dye. 

BENZIDIN, tolidin, or other diamino comp. coupled with 1 mol. each of saLicyzic acid and 
RESORCIN then combined in alk. soln. with diazo suLFANILIc acid, metanilic acid, or other. (b) 


Or components 1-2 are coupled with 3-4, previously coupled. Brown direct dyes. 
S. 477—‘‘Congo Brown G.” 


401,024—Apr. 9, 1880. Eugen Franx, Germany. (Bayer.) 
Yellow dye. 

TouipIn coupled with 2 mols. saticytic acid. A brown red pwd. sol. in hot soap soln. 
(Y), sol. conc. H,SO, (dark V); a yELLow direct dye, fast to soap and light, slightly redder 
than benzidin deriv. 

S. 394—‘‘Chrysamin R.”’ Note 320,638. 


401,483—Apr. 16, 1889. Theodor Drtu1t, Germany. (Zimmer.) 
Crimson dye. (Process also claimed.) 
BENzIDIN or other, coupled with 2 mols. phenyl 2-NAPHTHYLAMIN sulfo or 1 mol. each of 


above component and then with naphthionic, salicylic, 2-naphthol disulfo, or other phenol amin 
or their sulfo or carbo derivs. ORANGE, violet RED to blue vioLEt direct dyes. 


401,634—Apr. 16, 1889. Réne Boun, Germany. (Badische.) 
Carbazol-yellow. 

CaRBAZOLE converted to dinitro deriv. by adding HNO, to glac. acetic soln. at 50°, then 
heating to 100°, separated and reduced by Sn and HCl or Zn and alk., to diamino cARBAZOLE, 
which is purified, tetrazotized and coupled with 2 mols. saLticyntic acid. A YELLOW direct or 
acid dye. 

S. (4th ed.) 264—‘‘Carbazol Yellow.”’ 


402,980—May 7, 1880. J. Scumip, Switzerland. (Basle.) 
Azo dye. (Process, not product, claimed.) 
I-NAPHTHYLAMIN coupled with 3-amino PHENOL, or its alkyl derivs. in acetic or alk. soln. 


A green pwd., almost insol. aq., sol. in alc. and glac. acetic (OY); a RED dye used probably for 
coloring varnishes, fats and oils, etc. 


404,097—May 28, 1880. Adolf LiepmMann, England. 
Production of yellow coloring-matter. (Product, not process, claimed.) 

Dehydro thio 4-ToturpIn sulfo, or primulin, coupled with 2-NAPHTHOL and product refluxed 
in bisulfite soln. (50° Tw.) or treated with solid bisulfite. A yellow pwd., easily sol. aq., 
decomp. by caustic, sol. conc. H,SO, (VR) with evolution of SO,; a RED developed (steam) 
dye for printing. 

Near S. 193—‘“‘Clayton Cloth Red.”’ 


404,331—May 28, 1889. Re. 11,016—July 30, 1889. 
R. GrEVILLE-Wi.LiiaMs, New York. (Albany.) 
Compound orcin dye. (Process, not product, claimed.) 

Benzipin, tolidin, or sulfo derivs., coupled with 1 mol. each of 2-NAPHTHYLAMIN sulfo or 
other, in acetic soln. and orcin, or its sulfo derivs., in alk. soln. Products are insol. in dil. 
acids, sol. in conc. H,SO,. Rep to violet RED direct dyes. 

Note 394,425. 


406,669—July 9, 18809. T. SANDMEYER, Switzerland. (Bayer and Berlin.) 


Red color. (Process only claimed.) 


2-TOLUIDIN boiled with NaOH, an equal weight of NITROBENZENE slowly added, diluted, 
reduced with Zn powd., boiled in conc. HCl, and coupled with 2 mols. NAPHTHIONIC acid or 1 
mol. each of two coupling agents, amins, naphthols, their sulfo acids, etc. REp to vioLEer direct 
dyes. 


406,670—July 9, 1880. T. SANDMEYER, Switzerland. (Bayer and Berlin.) 


Yellow color. (Process only claimed.) 
2-TOLUIDIN boiled in NaOH soln., an equal weight of NITROBENZENE gradually added, product 
reduced with Zn powd., cooled, poured into conc. HCl, boiled, diluted, filt., pptd. by Glauber’s 


82 DIGEST OF PATENTS 


and as twenty per cent paste coupled in alk. soln. with sanicyzic acid, or other. YELLOW 
direct dyes. 


409,384—Aug. 20, 1880. C. S. Beprorp, England. 
Compound dye. (Process also claimed.) 
ANILIN, toluidine, naphthylamin, or other amin, coupled in alk. carb. soln. with ext. of 


FUSTIC, by mixing the acid diazo soln. thoroughly with the extract of the rasped wood, then 
making alk. YELLOW to BRown oil sol. dyes for coloring varnishes, etc. 


410,057—Aug. 27, 1880. R. GREvILLE-Wi1LLiamMs, New York. (Albany.) 
Process of making orcine dye. 

BENZIDIN, or other diamino comp., coupled with NapuHtTHioNnic acid or other sulfo acid, 
followed by methyl orcin sulfo acid or other alkylized orcin sulfo acid, mono, di-, tri-methyl, 
ethyl, amyl, or acetyl orcin. The intermediate, consisting of benzidin azo naphthionic acid, 
must always be added to orcin comp. in alk. soln., and must never be in excess. Rep direct 
dyes. 

Note 404,331 and 410,058. 


410,058—Aug. 27, 1880. R. GREVILLE-WiLLiams, New York. (Albany.) 
Process of making orcine-dyes. 

BENzIDIN, or other diamino comp., coupled with NapuHrHionic acid, followed by orcIn 
prepared as follows: Orcin five per cent in sat. NaCl soln., free of CaO, made slightly acid with 
HCl, boiled till green fluorescence shows when made alk. with NaOH, filt. and dried. The 
diazo benzidin azo naphthionic acid must always be added to the orcin soln. so that the latter is 
always in excess. Orange rep direct dyes, fast to washing. 

Note 410,057 and 404,331. 


412,148—Oct. 1, 1880. R. GREVILLE-WILLIAMS, New York. (Albany.) 
Process of making dyes. 

BeEnz1pIN, or other diamino comp., treated in alk. sol. with 2 mols. methyl orcHiL or other 
alkylized chlor. or sulfo deriv. of orchil. An orange rEp direct dye, fast to washing. 

Note 412,149. 


412,149—Oct. 1, 1880. R. GREVILLE-WILLIAMS, New York (Albany.) 
Process of making dyes. 

ToLIpIN, or other diamino comp., coupled with 1-NAPHTHYLAMIN sulfo, or other amin or 
phenol, followed by 1 mol. methyl orcHi1L, or deriv. A violet RED direct dye. 

Note 412,148. 


412,440—Oct. 8, 1880. A. WEINBERG, Germany. (Cassella.) 
Azo coloring-matter. 

NAPHTHYLAMIN 3.6-disulfo, or other naphthylamin sulfo, coupled with 1-NAPHTHYLAMIN, 
diazotized and again coupled with 1- or 2-NAPHTHYLAMIN. Products in acid soln. (B), sol. 
conc. H,SO, (GBk), sol. in aq., diff. sol. alc., decomp. by reducing agents; blue BLACK direct 
dyes, fast to washing and milling. 

S. 226—‘“‘Naphthylamin Black D.” Note 345,901. 


415,258—Nov. 19, 1889. M. Uxricu, Germany. (Bayer.) 
Azo-blue color. 
DIPHENETIDIN (diamino diphenol ether) coupled with 2 mols. 2-8-dioxy NAPHTHALENE 6-sulfo 


(prepared as in 415,257 from “‘G” acid). A black amorph. pwd., sol. in aq. (B), soln. not 
changed by alk., sol. conc. H,SO, (GB); a Biux direct dye, fast to soap and mineral acids. 


416,145—WNov. 26, 1889. R. GrEVILLE-WiIL11AMs, New York. (Albany.) 
Process of making azo dyes. 

NapuTHionic acid, or other, coupled in acetic soln. with a second mol. of same, to form 
amino azo naphthalene disulfo. Tonrp1n or other diamino comp. tetrazotized and coupled 
first with above, then with NAPHTHIONIC acid, or other amin or phenol. A rep direct dye, 
more soluble than Benzopurpurin 4B. 

Near S. 363—‘“‘Benzopurpurin 4B.” 


Eanes 


ee ee eee 


GROUP VI.—AZO 83 


416,145—WNov. 26, 1889. Re. 11,178—July 1, 1891. 
R. GREVILLE-WILLiAMs, New York. (Albany.) 
Manufacture of mixed azo colors. (Product also claimed.) 

NaAPHTHIONIC acid coupled in acetic acid soln. with naphthionic acid, 1 mol. of this com- 
bined in acetic acid soln. with tetrazo roxipin, or other diamino comp. and derivs., and finally 
coupled with a third mol. of NaApHTHIONIC acid. A brick red powd., sol. in aq., sol. conc. acid 
(B), but pptd. on diln., fiber blue with conc. H,SO, and brown with acetic; a rep direct 
dye. 


417,207—Dec. 10, 1880. R. GrevitLE-WiiLtams, New York. (Albany.) 
Process of making azo dyes. 


ToLIDIN or its homologs or derivs., coupled with NapuTHronic acid or other amin, then 
with diazo naphthionic acid and again with naphthionic acid, or other amin or phenol, their 
alkyl, sulfo, carbo, or oxy derivs. VARI-coLoRED direct dyes. 

Note patent is isomeric with 416,145. 


417,207—Dec. 10, 1889. Re. 11,179—July 21, 1891. 
R. GrEVILLE-WILLIAMS, New York. (Albany.) 
Manufacture of azo colors. 

To.ipIn, or other tetrazotizable diamin, coupled with NAPHTHIONIC acid, or other amin 
or deriv., then combined with diazo naphthionic acid, and finally the free diazo bond of first 
component coupled with more naphthionic acid or other amin, phenol, or derivs. Products are 
insol. in dil. acids, sol. in dil. alk. Rep direct dyes. 

Note 416,145, Re. 11,178. 


417,294—Dec. 17, 1889. M. Uxricu, Germany. (Bayer.) 
Azo dye. 

DIAnNIsipIN, coupled in alk. soln. with 2 mols. 1.8-dioxy NAPHTHALENE 4-sulfo (from Schoell- 
kopf’s acid “S” by fusion with alkali). A black amorph. powd., sol. in ag. (B), soln. with 
alk. (RV), sol. conc. H,SO, (deep GB), pptd. on diln. (B); a green siux direct dye, fast to 
soap and mineral acid. 

Note 417,295 and 417,296. 


417,295—Dec. 17, 1889. M. Utricz, Germany. (Bayer.) 
Azo dye. 

Brenzip1n coupled in alk. soln. with 2 mols. 1.8-dioxy NAPHTHALENE 4-sulfo from Schoell- 
kopf’s disulfo acid ‘‘S’’ by fusion with alkali). A black powd., easily sol. aq. (V), sol. conc. 
H,SO, (deep B), aq. soln. with alk. (R); a violet Bug direct dye, fast to soap and mineral acid. 

Note 417,294. ) 


417,296—Dec. 17, 18809. M. Uuricu, Germany. (Bayer.) 
Azo dye. 

2-TOLIDIN coupled in alk. soln. with 2 mols. 1.8-dioxy NAPHTHALENE 4-sulfo (from Schoell- 
kopf’s disulfo acids by fusion with alkali). A black amorph. powd., easily sol. cold ag. (V), 
with alk. (R), sol. conc. H,SO, (GB); a direct BLUE dye, fast to soap and mineral acid. 

Note 417,294. 


418,657—Dec. 31, 1880. Gustav ScuuLtz, Germany. 
Production of orange and red dye-stuffs. 

XyYLIDIN or other amino comp., 2 parts, heated with one part sulfur as long as H,S escapes, 
to form diamino dimethyl stiLBENE sulfide which is diazotized and coupled with 2 mols. 1- 
NAPHTHOL disulfo, then sulfonated or not. Second component may be a phenol, naphthol, 
orcin, resorcin, amino comp. or their sulfo or carbo acids. Vari-coLorED direct dyes, fast to 


acid, soap, and light. 
S. 121—“Erika B.”’ 


420,372—Jan. 28, 1890. O. N. Wirt, Germany. (Badische.) 
Blue dye. 

2-NAPHTHYLAMIN 6-sulfo (Brénner’s acid) coupled with 2-NAPHTH-HYDROQUINONE. A dark 
brown powd., easily sol. cold aq., soln. with HCl ppts. dye acid, with alk. turn blue and fades 
(decomp.), sol. conc. H,SO, (dark B); a dark BLUE (Cr) or blue vioret (Al) acid mordant dye 


or lake. 
Note 420,372 (Gr. XXII) for 2-naphth-hydroquinone and 420,374 for addition. 


84 DIGEST OF PATENTS 


420,374—Jan. 28, 1890. O. N. Witt, Germany. (Badische.) 
Dark-blue dye. 


I-NAPHTHYLAMIN 4.6- or 4.7-disulfo (Dahl’s acids), coupled with 2-NAPHTH-HYDROQUINONE 
sulfo or other. A brown powd. easily sol. cold aq., aq. soln. not pptd. by HCl except with 
large excess, soln. with alk. (OR to BG) then fades (decomp.), sol. conc. H,SO, (BV); a dark 
BLUE (Cr) or blue-vioteT (Al) acid mordant dye. 

Note 420,372. 


421,640—Feb. 18, 1890. A. WEINBERG, Germany. (Cassella.) 
Blue azo dye. (Process, not product, claimed.) 


ANILIN, naphthylamin, benzidin, or other amino comp., coupled with ethoxy 1-NAPHTHYLAMIN 
sulfo, or other oxyether of 1-naphthylamin or their sulfo acids, again diazotized and coupled 
with 2-NAPHTHOI, 4.8-disulfo or other amin or phenol. BLUE to GREEN direct dyes, fast. 


423,550—Mar. 18, 1890. C. Duisperc, Germany. (Bayer.) 
Process of making blue dyes. 


BENzip1In sulfone disulfo coupled in alc. soln. with 2 mols. of 4-tolyl 2-NAPHTHYLAMIN, OT 
I- or 2-naphthylamin and their sulfo derivs. Product is insol. in aq.; a BLUE direct dye. 


423,569—Mar. 18, 1890. P. Orr, Germany. (Bayer.) 
Azo dye. (Process, not product, claimed.) 


Diamino DIPHENYLENE oxide or the ditoluylene deriv., coupled with 2 mols. 1-NAPHTHYLAMIN 
or other amin or phenol, or other sulfo or carbo acid, or 1 mol. each of two different com- 
ponents including sulfo and carbo derivs. Products may be sulfonated, and thus made sol. in 
aq.; RED tO VIOLET direct dyes. 


423,970—Mar. 25, 1890. M. Uxricu, Germany. (Bayer.) 
Blue carbon dye. (Process, not product, claimed.) 


BENzIDIN, or other para diamin, coupled with 2 mols. 1.8-dioxy NAPHTHALENE 4-sulfo 
(obtained by heating 1-NAPHTHOL 4.8-disulfo ‘S’ with NaOH and excess carbonate), or other 
dioxy naphthalene sulfo acid. Buus direct dyes. 

Note 444,679 for mfr. of sulfo acid. 


424,019—Mar. 25, 1800. R. Nrerzxi, Switzerland. (Hé6chst.) 
Brown carbon dye. 


4-NITRANILIN or other nitro amino comp., coupled with saLicyzic acid or other ortho oxy 
carbo acid. Products are insol. in aq. or dil. acids, easily sol. in alc., ether or dil. alk., Ca 
salts diff. sol. hot aq., Ba salts almost insol., soln. of alk. salt pptd. by FeCl, (dark Br), CuSO, 
(YBr), Pb acetate (O), CrSO, (Y Br), sol. conc. H,SO, (Y), pptd. on diln.; yELLow to BRowN 
acid mordant dyes, especially fast on Cr and Ni mordants. 

S. 48—“Alizarin Yellow GG.” 


425,885—Apr. 15, 1890. M. Kaun, Germany. 
Proeess of making azo dyes. 


SuLFANILIC acid, or other sulfo acid of anilin, coupled with 1-NAPHTHYLAMIN then again 
diazotized and coupled with 4-tolyl 1-NAPHTHYLAMIN or a homolog.; a blue-BLack direct dye. 
S. 263—‘‘Jet Black R.”’ 


426,345—Apr. 22, 1890. A. WEINBERG, Germany. (Cassella.) 
Red dye. : 


BENz1pDIN or other, coupled with 2-NAPHTHOL 3.6-disulfo ‘“‘G,’’ then PHENOL, added, and soln. 
boiled. Pptd. dye is heated at 60° in fifty per cent alc. soln. containing NaOH with METHYL 
chloride, ethyl or benzyl halogen salt. A cryst. red powd., easily sol. hot aq., slightly sol. 
in alc., sol. conc. H,SO, (V), soln. decol. by reducing agents and decomp. into amins.; 
an orange RED direct dye, fast to acids. 

S. 319—“‘Diamin Scarlet B.” 


428,629—May 27, 1890. W. Pritzincer, Germany. (Bayer.) 
Substantive yellow dye. (Process, not product, claimed.) 


Thio 4-ToLuIpIN (dehydro thio toluidin sulfate) or other thio deriv. of 3-xylidin, ps-cumidin, 
or sulfo derivs., coupled with thio 4-roLurpIn sulfo or other thio derivs. and their sulfo acids. 
Green YELLOW to orange YELLOW direct dyes. 

S. 198—‘‘Clayton Yellow.” 


GROUP VI.—AZO 85 


429,350—June 3, 1890. G. Korrner, Germany. (Badische.) 
Red dye. 


2-3/-TOLIDIN coupled in acetic acid soln. with 2 mols. NAPHTHIONIC acid. A red brown 
powd., easily sol. hot aq., sol. in alc. (OR), insol. in benzene, dil. soln. with thirty per cent 
acetic acid (V), then pptd., with twenty-five per cent HCl] (B); a direct orange rED dye. 

S. 363—‘“‘Benzopurpurin.” Note 329,632. 


430,533—June 17, 1890. C. I. MU.ier, Germany. (Badische.) 
Process of preparing disazo dyes. 


4-Amino acetanilid, or other, coupled with saricyiic acid or other phenol or amino comp. 
or its sulfo or carbo deriv., saponified, and amino azo body suspended in slightly alk. soln., 
while PHOSGENE, CS,, C,H,Br,, or other gas, is added slowly to acid reaction, to condense a 


urea disazo body. <A direct YELLOW dye. 


430,534—June 17, 18090. C. L. Mtiier, Germany. (Badische.) 
Red to brown dye. 


4-Amino ACETANILID coupled with NAPHTHIONIC acid, saponified, the salt suspended in ag. 
and PHOSGENE added to acid reaction, to condense two amino azo comps. by means of the urea 
residue. A brown red powd., sol. in aq., alc. (OR) and H,SO, (VR), pptd. on diln. (B), 
aq. soln. pptd. with HCl (BV), with NaOH is unchanged; pale oRANGE (salmon) to BRowN direct 
dye. 

Note 430,535. 


430,535—June 17, 1890. C. L. Mtiuer, Germany. (Badische.) 
Yellow dye. 

4-Amino ACETANILID, coupled with saticyzic acid, saponified, and sodium salt suspended in 
aq. treated with PHOSGENE gas or liquid. <A dull yellow powd., sol. in aq. and alc. (Y), aq. soln. 
with HCl ppts. (dark RBr), and with NaOH is (OY), sol. in conc. H,SO,, (OR) and pptd. on 
diln. (Br); a direct yELLow dye. 

S. 296—‘“‘Cotton Yellow C.’’ Note 430,534. 


431,297—July 1, 1890. J. Water, Switzerland. (Geigy.) 
Azo color. (Process, not product, claimed.) 

Aniuin, naphthylamin, or other aromatic amin, coupled with saticyLic acid, or other 
aromatic acid, then nitrated. Nitro group probably becomes attached to the salicylic acid rest. 


YELLOW to BROWN acid mordant dyes. 
S. 58—“Alizarin Yellow R.” 


432,989—July 29, 1890. C. DuissErc, Germany. (Bayer.) 
Blue dye. 

Benzipin sulfate added to fuming sulf. acid (forty per cent anhyd.), to form the sulfone, 
then heated to 160° and the resulting BENzIpIN sulfone disulfo is diazotized and coupled with 
2 mols. phenyl 2-naphthylamin. An indigo blue amorph. powd., easily sol. hot aq. and alc., 
insol. in benzene, sol. conc. H,SO, (RV); a direct BLUE dye. 

S. 361—“Sulfon Azurin D.” 


438,438—Oct. 14, 1890. R. Laucu and C. KrexeiEer, Germany. (Bayer.) 
Manufacture of dyestuffs. (Product, not process, claimed.) 

Amino saLicyiic acid coupled with 1-NAPHTHYLAMIN then with 1-NaPHTHOL sulfo. A blue 
black paste or powd., easily sol. hot aq. (BV), aq. soln. with NaOH (GB), with mineral 


acid ppts. dye acid; a blue siacx direct dye adapted to printing cotton. 
S. 275—“Diamond Black F” and S. 276—“‘Diamond Green B.” 


440,288—Nov. 11, 1890. J. WALTER, Switzerland. (Geigy.) 
Brown dye. 
Naputuionic acid, amino azo benzene or toluene sulfo acids, coupled with 3-PHENYLENE 


DIAMIN or other meta diamin, then coupled with diazo PriMULIN. A brown powd., easily sol. 
aq., diff. sol. alc., slightly more so in methyl alc., insol. in benzene and ether, sol. conc. H,SO, 


(VR); a Brown direct dye. 
S. 209—‘Terracotta F.” 


86 DIGEST OF PATENTS 
440,639—Nov. 18, 1890. R. Laucu and M. Kaun, Germany. (Bayer.) 
Blue-black azo dye. ¢ 


BENzIDIN, or other diamino comp., coupled with 1-2 mols. 1-NAPHTHYLAMIN, again tetrazotized 
and coupled with 2 mols. 1-NAPHTHOL 4-sulfo or other naphthol sulfo acid. When 2 mols. 
naphthylamin take part in first coupling the product is sulfonated before further coupling, to 
render it soluble. Brown powd., sol. in hot aq. (V). insol. in ale. or benzene, sol. H,SO, (GB), 
and on diln. turns (RV) and ppts. (VB); vioLet to blue Biack direct dyes. 

S. 450—‘‘Benzo Black Blue R.” 


440,953—Nov. 18, 1890. W. Mayjert, Germany. 


Blue dye. (Process and intermediate claimed, not dye.) 

BENZIDIN or other diamino comp., coupled with 2 mols. 1.8-dioxy NAPHTHALENE (m.p. 
248-252°), or its sulfo acids, or with 1 mol. each of this component and a phenol, naphthol, sulfo 
acid, or other. Brive direct dyes. 
441,945—Dec. 2, 1890. 
Red dye. (Process also claimed.) 


C. Dreyfus, England. (Clayton.) 


Dehydro thio 4-ToLumpIn sulfo coupled with 2-NapuHtHoL, pptd. by HCl and dissolved in 
NH, to form salt more soluble than Na. Patent refers to two products formed, but only one 
is described. A red brown powd., sol. in aq. (R) and in alc. (R); a RED acid and acid mordant 
dye, suitable for printing. 

S. 193—‘‘Clayton Cloth Red.” 


442,369—Dec. 9, 1899. L. Gans, Germany. (Cassella.) 
Blue-black dye. 


BEnzIDIN or other diamino comp., coupled with Amino NAPHTHOL sulfo, 2 mols., or with 
1 mol. each of two different coupling agents. Products are sol. in aq., nearly insol. in alc., sol. 
in conc. H,SO, (B), and pptd. on diln; BLuE to BLAcK direct dyes. 

S. 402—“‘Diamin Black BO.” 


447,189—Feb. 24, 1891. Paul Jutius, Germany. (Badische.) 
Diamino DIPHENYL ketoxim tetrazotized and coupled with 2 mols. NaPHTHIONIC acid. A 
direct RED dye. 


447,302—Mar. 3, 1891. C. Dursserc, Germany. (Bayer.) 
Violet dye. 


DIANISIDIN, or homolog, coupled with 1-NAPHTHYLAMIN sulfo and then with 1-NAPHTHOL 
sulfo, or other. A green blue amorph. powd., easily sol. aq. (V), sol. conc. H,SO, (GB), 
pptd. on diln. (B); a direct vioLtet dye which when coppered becomes violet sLugE (acid mordant 
or developed dye). 

S. 407—‘‘Azo Violet.”? Note 447,303. 


447,303—Mar. 3, 1891. C. Duisperc, Germany. (Bayer.) 
Orange dye. (Process also claimed.) 

Benzip1n sulfate coupled with saticyntic acid, then with NAPHTHYLAMIN sulfo. A reddish 
amorph, powd., easily sol. in aq. (O), sol. conc. H,SO, (B), pptd. on diln. (Bk), aq. soln. with 
acetic or mineral acid ppts. (Bk); a red ORANGE direct dye. 

S. 340—‘‘Benzo Orange” and S. 341—‘‘Crumpsall Direct Fast Red R.” 


449,629—Mar. 31, 1891. J. Scumip, Switzerland. (Basle.) 
Black dye. 

I-NAPHTHYLAMIN 4.6- or 4.7-disulfo, ‘“‘Dahl’s,’”’ coupled with 1-NAPHTHYLAMIN, rediazotized 
and coupled with ethyl 2-NAPHTHYLAMIN, or other mono alkylized deriv. of 2-naphthylamin. A 
dark brown powd., easily sol. aq. (BBk), diff. sol. in alc., insol. in benzene, sol. conc. H,SO, 
(G), pptd. on diln. (BBk), aq. soln. not changed by alk., pptd. by mineral acids; BiacKx direct 
dyes, in light shades a blue Gray. 

Near S. 267, 268, or 2609. 


452,197—May 12, 1801. J. Scumip, Switzerland. (Basle.) 
Orange-yellow dye. 

4-Amino Saxicytic acid, or homologs, obtained by reduction of nitro comp., coupled with 
RESsoRCIN, in NH, soln. Orange brown paste or powd., easily sol. in aq. (OY), and alc. (Y), 


ag 


a ee ee ee 


. 
—_—s 


ae 


GROUP VI.—AZO 87 


\ 


insol. in benzine or ether; orangge yELLOw (Cr) or BRowN (Fe) acid mordant dyes, fast to 
soap and milling. 


454,645—June 23, 1801. Teo Gans, Germany. (Cassella.) 
Amido-naphthol-monosulphonie acid. (Process and products, for dyes, claimed.) 
4-NITRANILIN, 2-naphthylamin disulfo, amino azo benzene disulfo, benzidin, or other, coupled 
with 2-AMINO 8-NAPHTHOL 6-sulfo. VaARI-cOLORED acid or direct dyes. 
Near S. 333, 343, 344, 403, etc. Note 442,369. 


454,840—June 30, 1891. O. BorGMANN, Germany. (Berlin.) 
Orange dye. (Process also claimed.) 

BENzIDIN, or homolog, coupled with 1 mol. each of 2-NAPHTHYLAMIN 3.6- disulfo “‘R’ and 
PHENOL (as in patents issued to Jensen, Martius, etc.), then alkylated by refluxing in fifty 
per cent alc. NaOH with EruyLt bromide, methyl iodide, or other, to form ethoxy comp. Im- 
proved fastness to alk. claimed. Amorph. orange red powd., easily sol. hot aq. (OR), slightly 
sol. hot alc., aq. soln. with acetic turns (Br), ppts. with conc. minegal acids (Br), with NaOH 
is not changed but excess gives gel (OR), sol. conc. H,SO, (B), pptd. on diln. (Br.), decomp. 
on reduction; orange YELLOW direct dyes. 

S. 315—‘‘Congo Orange G.”’ 


456,627—July 28, 1891. C. A. Martius, Germany. (Berlin.) 
Process of making azo dyes. 

XyLipIn, or other amino comp., coupled with 1-NaPHTHOL 4.8-disulfo “S’ (list of other 
components and colors produced on fiber); RED BROWN, VIOLET or BLACK—VARI-COLORED acid 
dyes. 

S. 80—‘‘Wool Scarlet R.”’ Note 456,628. Is this a duplication of 333,035 (Mensching)? 


456,628—July 28, 1891. C. A. Martius, Germany. (Berlin.) 
Process of making azo dyes. 

DIAMINO STILBENE or other diamino comp., coupled with 1-naphthol 4.8-disulfo “S” in 
acetic acid soln. then with another mol. of same in alk. soln. For second components other 


naphthols or their mono or disulfo derivs. may be used. Blue vioxet direct dyes. 
Addition to 456,627. 


456,897—July 28, 1801. C. A. Martius, Germany. 
Azo dye. (Process, not product, claimed.) 

Xyiipin diamino stilbene, or other mono or diamino comp., coupled with 1-NAPHTHOL 
4.8-disulfo. List of other components, and color of dyes produced is given. VaARI-coLORED 
acid dyes. 

Near S. 77—‘‘Azo Coccin 2 R.” Note 456,627 among Intermediates. 


458,283—Aug. 25, 1891. Re. 11,231—Apr. 5, 1892. H. Kuzeit, Germany. (Hodchst.) 
Azo dye. 

ANILIN or any amino comp. or sulfo deriv., coupled with 1.8 dioxy NAPHTHALENE 3.6-disulfo. 
Brown powds., easily sol. in aq. (BR) in dil. acids and in alc., insol. in ether or ligroin; 
violet RED acid dyes or dark violet rep (Al or Cu) or vioret (CrAl) or Brack (CrO,) acid 
mordant dyes, fast to light and alk. 

S. 40o—‘‘Chromotrop 2 R.’’—Note 360,968 for new disulfo acid employed. 


458,284—Aug. 25, 1891. H. Kuzer, Germany. (Héchst.) 
Azo dye. 

Anitin or other amino deriv., coupled in dil. NaOH or Na acetate or carbonate, with 
NAPHTHOL trisulfo monamid. Dark red brown powds., easily sol. in aq. (R), insol. in alc., 


sol. conc. H,SO, (OR); a violet RED acid dye. 
Note Ser. 361,722, (this pat. Ser. 361,723). 


462,414—Nov. 3, 1891. C. Rupotpy, Germany. (Oehler.) 
Brown dye. 


4-Amino ACETANILID, 2 mols. coupled in alk. soln. with 1 mol. 3-PHENYLENE DIAMIN, then 
dye pptd. with ZnCl,. A black powd., easily sol. in aq. soln. with NaOH ppts. (Br), is decomp. 
by Zn and HCl, sol. in conc. H,SO, (BrR); a Brown basic dye. 


88 DIGEST OF PATENTS 


462,415—Nov. 3, 1801. C. RupotpH, Germany. (Oehler.) 
Blue-black azo dye. 

TouipIn, or benzidin, coupled with 1-Am1INo 8-NAPHTHOL 3.6-disulfo in alk. soln., then with 
I- OF 2-NAPHTHYLAMIN in acid soln. Bronze or dark brown powds., sol. in aq. (RV), aq. soln. 
with conc. HCl gives ppt. (RV-BV) with NaOH no change or (dull V), sol. in conc. H,SO, 
(B); a blue sracx direct dye. 

S. 382—‘‘Azo Mauve B.”’ Note 608,999. 


462,824—WNov. 10, 1891. ‘ G. Scuuttz, Germany. (Berlin.) 
Blue azo dye. (Process also claimed.) 

ToLip1In, or other diamino comp., coupled with 1-NAPHTHYLAMIN, re-diazotized and coupled 
with 2 mols. 1-NAPHTHOL 4.8-disulfo “D” or “E” (1.2.8), or other phenol, amin or their 
sulfo or carbo derivs. or alkyl ethers. Products are easily sol. in aq. and conc. H,SO,, insol. in 
alc.; VARI-COLORED direct dyes. 

Near S. 382—‘‘Azo Mauve B.” For sulfo acids, see 333,034 and 405,938. 


464,135—Dec. 1, 1891. M. Horrman, Germany. (Cassella.) 
Blue dye. (Process also. claimed.) 


BEeNzIDIN or other para diamin coupled with 2 mols. 1-AMINO 8-NAPHTHOL 3.6-disulfo. A 
dark bronze powd., easily sol. in aq. (B), insol. in alc. or ether, aq. soln. not changed by 
Na,CO,, sol. conc. H,SO, (B), ppts. on diln. (VB) as free dye acid; a direct Bur dye, fast 
to alk. and acids. 

S. 426—“‘Diamin Pure Blue.” 


464,566—Dec. 8, 1801. M. Horrman, Germany. (Cassella.) 
Violet dye. 


1.5-DIAMINO NAPHTHALENE 3.7-disulfo, coupled with 2 mols. 1-NAPHTHYLAMIN in aq. or 
alc. soln. Product is easily sol. in hot aq. (V), in conc. H,SO, (dark B), decomp. by reducing 
agents into two amino comps.; a vioLEet direct dye that may be diazotized and developed on 
the fiber by phenols or amins. 

S. 432—“‘Diamin Catechu.” or “Naphthalene Violet.’”? Note 472,121 and 473,928 (as de- 
veloped dye). 


464,775—Dec. 8, 1801. R. Laucu and C. Krexeier, Germany. (Bayer.) 
Blue-green azo dye. (Process also claimed.) 


Amino saLicyyLic acid coupled in acetic soln. with I-NAPHTHYLAMIN, again diazotized and 
coupled with 1.8 dioxy NAPHTHALENE 4-sulfo “S’? (see 444,679) in acetic soln. A blue black 
powd., sol. in hot aq. (BV), sol. dil. alk. carb. (BV), sol. dil, NaOH and NH, (B), in conc, 
H,SO, (G), pptd. on diln. (B), aq. soln. pptd. by mineral acids (B); a blue Green acid mordant 
(Cr) dye, fast to light, soap and milling. 

S. 276—‘“‘Diamond Green B.” Note 438,438 is patent number given by Schulz. 


465,116—Dec. 15, 1801. C. RupotpH, Germany. (Oehler.) 
Brown azo dye. (Process also claimed.) 

2.6-TOLUYLENE DIAMIN 4-Sulfo coupled with 2 mols. 3-PHENYLENE DIAMIN and again coupled 
in acetic soln. with 2 mols. NAPHTHIONIC acid or other naphthylamin sulfo acid. A green 
black powd., sol. in aq. (Br), in conc. H,SO, (dark VR), aq. soln. not changed by alk., free 
dye acid diff. sol. in aq.; a BRowN direct dye. 

S. 488—“Toluylene Brown R.”’ 


466,202—Dec. 29, 1891. M. Utricu, Germany. (Bayer.) 
Black azo dye. 

SULFANILIC acid coupled in acetic soln. with I-NAPHTHYLAMIN, again diazotized and coupled 
with 1.8-dioxy NAPHTHALENE 4-sulfo ‘‘S” in acetic soln. A green black powd., easily sol. hot aq. 
and hot alk. carb. (deep V), in hot dil. NaOH or NH, (B), in conc. H,SO, (G), pptd. on 
diln. (V flakes); a blue-black to Brack direct dye, fast to light, soap and milling and suitable 
for lakes (Cr). ; 

S. 262—‘‘Victoria Black B.”’ 


466,841—Jan. 12, 1892. M. Uxricu, Germany. (Bayer.) 
Red azo dye. 

To.uipin sulfo coupled in acetic acid soln. with 1.8 dioxy NAPHTHALENE 4-sulfo. A gray- 
violet amorph. powd., easily sol. aq. (VR). in dil. NaOH or NH, (R), in conc. H,SO, (BV); a 
violet RED acid dye. 

S. 71—‘‘Azo Fuchsin B.” S. 146 “Azo Fuchsin G.” For mfr. of sulfo acid, see 444,679. 


a NS 


- 


ee ee 


—o oF 


GROUP VI.—AZO 89 


467,162—Jan. 19, 1892. C. Duisserc, Germany. (Bayer.) 
Tetrazo dye. (Process also claimed.) 

DIANISIDIN coupled in acetic acid soln. with 2-NAPHTHOL 3.6-disulfo and then in alk. soln. 
with 1-NAPHTHOL 4-sulfo. Detailed comparison with closely related dyes patented by inventor 
and others is given. A blackish brown amorph. powd. with coppery luster, sol. in hot aq. (GB), 


in dil alk. (VR), in NH, (RV), in conc. H,SO, (GB) pptd. on diln. (B flakes), aq. soln. pptd. 
by mineral acids (B); a green sure direct dye. 
S. 412—“‘Congo Blue 2B.” 


468,049—Feb. 2, 1892. : C. Rupotpu, Germany. (Oehler.) 
Azo dye. 

ToLIpDIN or bezidin coupled in two per cent NaOH with 1-amMiIno 8-NAPHTHOL 3.6-disulfo 
“H” and with 3-oxy DIPHENYLAMIN or 3-oxy tolylphenylamin in alk. soln. A blackish powd., 


with metallic luster, sol. in aq. (dark V), in conc. H,SO, (B), decol. by reducing agents; a 
dark vioLet direct dye. 
S. 391—‘‘Azo Black Blue B.” 


468,142—Feb. 2, 1892. M. Utricu, Germany. (Bayer.) 
Blue-red azo dye. (Process also claimed.) 


SULFANILIC acid coupled with 1.8-dioxy NAPHTHALENE 4-sulfo. A violet red amorph. powd., 


easily sol. in aq. (VR), in alk. carb. or NH, (VR), in conc. H,SO, (VB); a violet rep acid, 
or dull vioLET acid mordant dye. 
S. 71—“‘Azo Fuchsin B” and S. 146—‘‘Azo Fuchsin G.” 


468,539—Feb. 09, 18092. O. Borcmann, Germany. (Berlin.) 
Red dye. (Process also claimed.) 

To.ipIN or benzidin coupled in acetic acid soln. with 2-NAPHTHYLAMIN 3.6 disulfo, ‘‘amino 
R acid,” and then in same soln. with NapHtTHONIC acid, and finally neut with alk., salted 
out, etc. A red powd., easily sol. in hot aq., insol. in alc., aq. soln. pptd. by alk., sol. conc. 
H,SO, (GB), decomp. on reduction; a Rep direct dye (bath containing sodium phosphate, 
carbonate, borate or stannate). 

S. 3690—“Brill. Purpurin.” 


472,121—Apr. 5, 1802. M. HorrMann, Germany. (Cassella.) 
Manufacture of yellow dyes. (Product, not process, claimed.) 


1.5-Diamino NAPHTHALENE 3.7-disulfo coupled in alk. carb. soln. with 2 mols. PHENOL, or 
homolog, then alkylated in alk. soln. with rruyLt chloride, or other alkyl halogen. A yellow 
powd., easily sol., in aq., diff. sol. in alc., sol. in conc. H,SO, (V), pptd. as free dye acid on 
diln. (dark G) and further diln. gives yellow soln.; a yELLow direct dye made fast to alk. by 
alkylation. 

S. 431—‘“‘Diamin Gold Yellow.’? For mfr. of sulfo acid, see 464,566. 


472,121—Apr. 5, 1892. Re. 11,267—Sept. 6, 1892. M. Horrmann, Germany. (Cassella.) 
Manufacture of yellow dyes. (Product also claimed.) 


1.5 Diamino NAPHTHALENE 3.7- disulfo coupled in alk. carb. soln. with 2 mols. PHENOL or 
other, and product alkylated in alk. alc. soln. with eruyz chloride or other alkyl halogen, to 
render dye faster to alk. The product is sol. in aq., diff. sol. in alc., sol. in H,SO, (V), on 
diln. ppts. (G), on further diln. the ppt. is sol. (Y); a direct yELLow dye, rendered fast to 
alks. by alkylation. 

S. 431—“‘Diamin Gold Yellow.’’ Addition to 464,566. 


473,928—May 3, 1892. M. Horrmann, Germany. (Cassella.) 
Process of dyeing black. 

“NAPHTHALENE VIOLEt (made from 1.5-NAPHTHALENE DIAMIN 3.7-disulfo coupled with 2 
mols. 1-NAPHTHYLAMIN in aq. or alc. carb. soln.) dyed on cotton or wool fiber, diazotized there- 
on and coupled in alk. bath with 2 mols. 2-NAPHTHOL or other oxy, dioxy, amino or diamino 
comp. or their sulfo derivs. Buacx developed dyes. 

S. 432—“Diamin Catechu.” For mfr. of dye as direct dye, see 464,566. 


90 DIGEST OF PATENTS 


476,335—June 7, 1892. Re. 11,308—Feb. 21, 1893. M. Uuricu, Germany. (Bayer.) 
Violet azo dye. (Process also claimed.) 

4-Amino PHENOL coupled with 1.8-dioxy NAPHTHALENE 4-sulfo “‘S.”” A dark brown powd., 
very sol. hot aq. (VR), which ppts. with acids (VR), sol. in alk. (OR), in conc. H,SO, (VB), 
pptd. on diln. (YBr flakes) to clear soln. (R); a vioueT acid dye, fast to air and light. 

Note 444,679. 


476,336—June 7, 18092. M. Utricu, Germany. (Bayer.) 
Black azo dye. (Process also claimed.) 

2-NAPHTHYLAMIN sulfo coupled with 1-NAPHTHYLAMIN then diazotized and coupled in acetic 
soln. with 1.8-dioxy NAPHTHALENE 4-sulfo “S.’? A brown black powd., sol. in hot aq. (GBk), 
pptd. by acids, sol. in alk. carb. caustic or NH, (dark B), sol. conc. H,SO, (G), pptd. on diln. 
(B flakes); a green BLacK acid or acid mordant (Cr) dye. 


476,337—June 7, 18092. M. Uuricu and R. Laucu, Germany. (Bayer.) 
Blue dye. 

DIANISIDIN coupled in HCI soln. with 1 mol. 1-NAPHTHYLAMIN, again diazotized and coupled 
with 2 mols. 1.8-dioxy NAPHTHALENE 4-sulfo in acetic acid soln. A gray black powd. sol. in 
hot aq. and sod. carb. (B), in dil. NaOH or NH, (B), in conc. H,SO, (GB), pptd. on diln., 
aq. soln. pptd. by acids (B flakes); a BLux direct dye. 


476,371—June 7, 1892. C. Duisperc, Germany. (Bayer.) 
Tetrazo blue dye. (Process also claimed.) 

DIANISIDIN coupled in acetic acid soln. with 2-NAPHTHOL 3.6-disulfo “R’” then in alk. 
carb. soln. with 1-NAPHTHOL 5-sulfo ‘“‘Cleve’s.’? A violet black powd., sol. in aq. (VB), soln. 
reddened by alk., sol. in conc. H,SO, (dark B), pptd. on diln.; a Brug direct dye greener 
than similar color from naphthionic acid. 


476,393—June 7, 1892. R. Laucu, Germany. (Bayer.) 
Dye-stuff. (Process also claimed.) 

BrenzipIN coupled in alk. carb. soln. with sanicyLtic acid and then in HCl soln. with 
I-NAPHTHYLAMIN, then sulfonated in fuming H,SO, (twenty per cent SO,) at 0-30°, and again 
coupled with 1-NAPHTHOL 4-sulfo ““NW.”’ A green black amorph. powd., easily sol. in aq. 
(Gy-Bk), in NaOH (R), in conc. H,SO, (YR), changing to (GB) on diln.; a green BLACK or 
dark gray direct dye, fast and of high tinctorial power. 

S. 447—‘“‘Dense Gray S ext.’”? Note 479,515. 


479,515—July 26, 1892. R. Laucu, Germany. (Bayer.) 
Olive dye. (Process also claimed.) 

Benzip1n coupled in alk. soln. with sanicyLic acid, then in HCI soln. with 1-NAPHTHYLAMIN. 
Product is sulfonated in fuming H,SO, (twenty per cent anhyd.) below 20°, the sulfo acid 
diazotized and coupled in alk. carb. soln. with 1.8 dioxy NAPHTHALENE 4-sulfo. Product may 
again be sulfonated. A brown to gray black powd., sol. in hot aq. and in dil. alk. carb. (GBr) 
turning BrR with excess carbonate, sol. in NaOH and NH, (BrR), soln. pptd. by acids (GyG), 
sol. in conc. H,SO, (V), pptd. on diln. (dark G); a brownish GREEN direct dye. 

Near S. 446—“Benzo Olive.’”’ Note 476,393. 


480,326—Aug. 9, 1892. M. Horrmann, Germany. (Cassella.) 
Diazo dye. (Product also claimed.) 

4-NITRANILIN or other nitro amino comps., coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo 
“H” in HCl soln., then coupled in alk. soln. with diazo ANILIN or other amin or sulfo acid. 
Green black powd., easily sol. in aq. (B), diff. sol. in alc., sol. conc. H,SO, (G), pptd. on diln. 
(B); blue Brack direct dye, the fastness of which is increased by after chroming. 

S. 217—‘‘Naphthol Blue Black S.” 


481,934—Sept. 6, 1892. C. Duissrerc, Germany. (Bayer.) 
Red dye and process of making the same, 


Diantisip1n coupled in acetic soln. with 2 mols. NAPHTHIONIC acid. A dark brown amorph. 
powd., easily sol. in aq. (VR), in conc. H,S0O, (B), pptd. on diln. (B); a violet RED direct dye. 
S. 405.—‘“‘Benzopurpurin 10B.’”’ Note 357,274 for similar dye. 


GROUP VI.—AZO QI 


482,106—Sept 6, 1892. M. Uxricu and J. BamMann, Germany. (Bayer.) 
Azo coloring-matter. (Process also claimed.) 

Benzip1n coupled in HCl soln. with 1-NAPHTHYLAMIN, tetrazotized and coupled with 2 mols. 
I-AMINO 8-NAPHTHOL 3.6-disulfo “H.” A gray black powd., easily sol. hot aq. (B), pptd. by 
acids (B), so]. in alk. carb. and NH, (B), in NaOH (VB), in conc. H,SO, (GB), pptd. on diln, 
(B); a green sive direct dye that may be diazotized on fiber and developed ch 2-naphthol to 
BLACK dye, fast to light, soaping and fulling. 

S. 441—“Diazo Blue Black RS.’”’ Note 462,415 and 462,864. 


483,368—Sept. 27, 1892. D. A. RosENSsTIEHL, France. 
Process of making azo colors. 

4-NITRANILIN or other nitramin coupled with NapuHruo. disulfo, or other phenol, amin, 
sulfo carbo or oxy deriv., then heated at 80° in an alk. glucose soln. or other alk. reducing 
agent. BLUE, VIOLET, RED, Of VARI-COLORED direct dyes. 

Near S. 483—‘“‘Rouge de St. Denis,”? or S. 484— ‘“‘Milling Scarlet.” 


484,521—Oct. 18, 1892. H. Kizzer, Germany. (Héchst.) 
Yellow dye-stuff. 

BeEnzip1n sulfone or other diamino sulfone or derivs., coupled in alk. carb. or acetic soln. 
with 2 mols. 2-cRESOTINIC acid, or other mono or dioxy carbo. acids. Orange-brown powd., 
diff. sol. in aq.» insol. in CHCl,, ligroin, CS,, sol. in dil. alks., ether, alc. and acetone; YELLOW 
acid mordant (Cr) dye, fast to fulling, soap, light and suitable for printing. 


491,410—Feb. 7, 1893. T. DieHt, Germany. (Berlin.) 
Blue-black azo dye. 

4-NITRANILIN coupled with 1-NAPHTHYLAMIN, nitrated and reduced to form 4-phenylene 
diamin azo 1-naphthylamin, then tetrazotized, and coupled with 2 mols. of 2-AMINO 8-NAPHTHOL 
6-sulfo “‘G’’ or other naphthol sulfo acid. A brown black powd., sol. in aq., sparingly sol. in 
alc., in conc. H,SO, (B) pptd. on diln.; blue BLack or violet BLACK direct dyes, fast to light, 


air, and soap. 
S. 245—“Nyanza Black B.” Note 458,285 and 511,688. 


491,422—Feb. 7, 1803. R. GnEHM and J. Scumip, Switzerland. (Basle.) 
Brown dye. 

3-Amino BENZOIC acid, 2 mols., coupled in acetic soln. with BISMARCK BROWN J or R (by 
action of HNO, on 3-PHENYLENE DIAMIN or homolog) and sol. alk. salt formed. A dark brown 
powd., sol. in aq., diff. sol. in alc. (BrO), sol. in conc. H,SO,, pptd. on diln., insol. in benzene; 


dark yellow Brown direct dye. 
S. 486—“Direct Brown J.” 


493,413—Mar. 14, 1893. B. R. Serrert, Germany. (von Heyden.) 
Dye from alpha oxyuvitie acid. (Process, not product, claimed.) 


BENZIDIN, or other mono or diamino comp. (see list of 52), coupled with 2 or 1 mols. of 
a-oxy uvitic acid in alk. soln. to form meta oxy azo comps. VARI-COLORED direct and acid 


mordant dyes. 


493,563—Mar. 14, 1893. J. Scumip, Switzerland. (Basle.) 
Blackish-blue azo dye. (Process also claimed.) , 

DIANisIpIN, or other para diamin, coupled with sulfo dioxy NAPHTHOIC acid then with 
I-NAPHTHOL 4-sulfo “NW” in alk. soln. A gray black sparkling powd., easily sol. aq. (dark B), 
in conc. H,SO, (GB), diff. sol. alc., insol. in ether and benzene; dark BLUE to dark vio." direct 
dyes. 

S. 428—“Direct Blue.” Note 493,564 for addition. 


493,564—Mar. 14, 1893. J. Scumip, Switzerland. (Basle.) 
Gray-black tetrazo dye. (Process also claimed.) ' 
Benzipin or tolidin, coupled in alk. carb. soln. with 2 mols. sulfo dioxy NAPHTHOLIC acid. 
Near S. 354—“Direct Gray R” and S. 397—“‘Direct Blue R.” 
7 


92 DIGEST OF PATENTS 


493,583—Mar. 14, 1893. R. GneuM and J. Scumip, Switzerland. (Basle.) 
Red dye. (Process also claimed.) 


2-Nitro BENzIDIN, coupled in alk. carb. soln. with sanicynic acid and in same soln. with 
I-NAPHTHOL 4-sulfo “NW.” A red-brown powd., easily sol. hot aq. (OR), diff. sol. in alc., 
insol. in benzine; an orange RED acid or dark rED acid mordant (Cr) dye, fast to air, soap, 
fulling, Cl and SO,. 

S. 355—‘‘Anthracene Red.” 


496,392—May 2, 1893. J. BaMMANN and M. ULricu, Germany. (Bayer.) 
Tetrazo dye. (Process also claimed.) 


Ethoxy BENzIDIN coupled in alk. soln. with 2 mols. 1-AMINO 8-NAPHTHOL 3.6-disulfo, ‘‘H.” 
A gray black powd., sol. in alk. carb. or NH, (B), in caustic alk. (V), in aq. (B), soln. not 
changed by strong mineral acids, pptd. from soln. by salt (B), sol. conc. H,SO, (B), pptd. 
on diln.; a green BLUE direct dye, fast to alk. 


497,032—May 9g, 1893. C. Rupotpu, Germany. (Oehler.) 
Orange azo dye. (Process also claimed.) 


2.6-TOLUYLENE DIAMIN 4-sulfo, coupled with 2 mols. 2-NAPHTHYLAMIN. One mol. combines 
first in HCI soln. to form a brown powd., then excess of sodium acetate and soda are added 
and heat applied. A red powd., sol. in hot aq. (OR), in conc. H,SO, (BGy), pptd. on diln., 
aq. soln. pptd. by HCl (Br); an orance direct dye. 
S. 287—“Toluylene Orange RR.” 


? 


498,303—May 30, 1893. E. von Porrueim, Austria-Hungary. 
Glycine dye. (Process also claimed.) 

Benzip1n or other dipara diamin, homologs or derivs., coupled in alk. acetate or alc. soln. 
with 2 mols. 2-NAPHTHYL glycin or 1 mol. 2-NAPHTHYLAMIN 2-sulfo and 1 mol. of 1-NAPHTHOL 
glycin, or other phenols, naphthols, amins, their sulfo acids and other glycins. Products are 
sol. in aq., more or less sol. in alc., not readily affected by alk.; BLUE to RED direct dyes. 

S. 310—“‘Glycin Corinth.” 


498,404—May 30, 1893. ‘ P. Ort, Germany. (Bayer.) 
Greenish-blue dye. 

ANILIN, coupled in acetic acid soln. with 1-NAPHTHYLAMIN 6- or 7-sulfo ‘‘Cleve’s,” re- 
diazotized and coupled with 4’-tolyl 1-NAPHTHYLAMIN 8-sulfo, also in acetic soln. A violet 
black powd., sol. in aq. (dark B), not changed by dil. NH, or alk. carb., but pptd. by excess 
(B flakes), pptd. by alk. caustic (B), pptd. by mineral acid slowly (B), sol. in conc. H,SO, 
(B), pptd. on diln. (B); a green BLuE direct dye. 

Near S, 242—‘“‘Sulfon Black G.”? Note 498,405. 


498,405—May 30, 1893. P. Orr, Germany. (Bayer.) 
Disazo dye. (Process also claimed.) 

AniuIn or deriv., coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo “Cleve’s,” rediazotized and 
coupled with phenyl 1-NAPHTHYLAMIN 8-sulfo (formed as in 498,404, with anilin instead of 
toluidin), An olive black powd. of metallic luster, sol. in aq. (V), not changed by dil. alk. 
carb. or NH, but pptd. by excess (VB), with NaOH pptd. (B) and by mineral acids (GB), 
sol. in conc. H,SO, (GB), pptd. on diln. (B); a violet snug direct dye, fast to washing, full- 
ing, light and alk. : 

Addition to 498,404. 


498,759—June 6, 1893. J. BammMann and M. Utricu, Germany. (Bayer.) 
Blue substantive dye. (Process also claimed.) 

2-TOLIDIN coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo ““H” in weak acid or alk. soln. and 
dioxy NAPHTHALENE in acetic soln. A gray black powd., sol. in aq. (V), slightly sol. in alc. 
(B), sol. in NH, (B), diff. sol. cold alk. carb. (V) on heating (B), slightly sol. NaOH 
(V to VR), sol. conc. H,SO, (GB), pptd. on diln. (B), insol. dil. mineral acids; a BLUE direct 
dye that may be diazotized on fiber and developed by 2-naphthol to form a deep BLUE to BLACK 
color. 

Note, 498,873 and 499,198, 544,699 and 544,700. 


GROUP VI.—AZO 93 


498,873—June 6, 1893. J. BaAmMann and M. Utricu, Germany. (Bayer.) 
Blue tetrazo dye. (Process also claimed.) 

2-TOLIDIN coupled with 1 mol. each of 1-AMINO 8-NAPHTHOL 3.6-disulfo and 1-NAPHTHOL 
4-sulfo, both in alk. soln. Other components claimed in other patents enumerated. A gray 
black powd., sol. in aq., slightly sol. ale. (VR) sol. in NH, alk. carb. and caustic (VR) but 
pptd. slowly (Br), sol. conc. H,SO, (GB), pptd. on diln. (B); a BLuxE direct dye that may 
be diazotized and developed on fibers by 2-naphthol to give blue Gray to BLACK shades. 

Note 464,135, 498,873 and 499,198. 


498,874—June 6, 1893. J. BAMMANN and M. Uuricu, Germany. (Bayer.) 
Blue tetrazo dye. (Process also claimed.) 

DIANISIDIN or homolog, coupled in alk. soln. with 2 mols. 1-AMINO 8-NAPHTHOL 3.6-disulfo 
“H.” <A red black powd., sol. in aq. (GB), in alk. carb. and NH, (GB), in caustic (V), aq. 
soln. only changed by excess alk. or NH,, unchanged by strong mineral acids but pptd. by 
salt (B), sol. in conc. H,SO, (BG), pptd. on diln. (B); a green siueg direct dye, fast to alk. 

S. 426—“Diamin Pure Blue.” Note 496,392 and 498,873 for homologs, also 262,135. 


498,982—June 6, 1893. C. KrexreLer and P. Krais, Germany. (Bayer.) 
Red dye. (Process also claimed.) 

Amino BENzoIC acid coupled in alk. carb. soln. with 1-NaApHTHOL 5-sulfo. A dark red 
powd., sol. in ag. (R), turned slightly yellower by NH, alk. carb. or caustic, pptd. by salt 
or conc. HCl, sol. in alc. (OR), in conc. H,SO, (VR), yellower on diln., sol. in NH, alk. carb. 
and NaOH (R), sparingly sol. dil. acids (R); a RED acid mordant (Cr) dye, suitable for print- 
ing. 
499,198—June 13, 1893. ' J. Bammann and M. Utricu, Germany. (Bayer.) 
Blue tetrazo dye. (Process also claimed.) 

Benzip1n or other, coupled in weak acid or alk. soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo 
“H,” then in alk. soln. with 1-NAPHTHOL 4-sulfo. A gray black powd., sol. in aq. (VR), and in 
NH,, alk. carb. and caustic (VR), slightly sol. in alc. (VR), insol. in dil. mineral acids, sol. 


conc. H,SO, (GB) pptd. on diln. (B); a BLue direct dye. 
Near S. 336—‘“‘Benzocyanin R.” 


499,216—June 13, 1893. C. Duisserc, Germany. (Bayer.) 
Blue tetrazo dye. (Process also claimed.) 

Benzipiw sulfone disulfo coupled in acetic soln. with 2 mols. ethyl 2-NAPHTHYLAMIN. 
A sivur black powd., sol. in aq. and alc. (VB) and in NH, (B), little sol. in alk. carb., 
almost insol. in dil. HCl or H,SO,, sol. in conc. H,SO, (VR), pptd. on diln. (VR); a direct 


violet BLUE dye. 
S. 361—‘“‘Sulfone Azurine D.” 


500,761—July 4, 1893. A. G. Green and T. A. Lawson, England. «(Brooke.) 
Red azo dye. (Process also claimed.) 

4-Nitro 2-To.uipin reduced with sodium stannite in alc. or aq. soln. to amino azo or amino 
azoxy compound, then coupled in alk. carb. soln. with 2 mols. 1-NAPHTHOL 4-sulfo (Piria) or 
with one mol. each of two different phenols, amins, or sulfo or carbo acid derivs. Bronze red 
powd., sparingly sol. in aq., insol. in alc., sol. in conc. H,SO, (VR), easily sol. dil. NaOH 
but pptd. on standing; YELLOW, ORANGE to RED direct dyes. 

Near S. 72—‘“Pigment Orange R.” 


500,762—July 4, 1893. A. G. Green and T. A. Lawson, England. (Brooke.) 
Red azo dye. (Process also claimed.) 


Amino azoxy ToLUIDIN coupled in acetic soln. with I-NAPHTHOL 4-sulfo then in alk. carb. 
soln. with 2-NAPHTHOL 3.6-disulfo “R.’” A dark red powd., easily sol. in aq., insol. in alc., aq. 
soln. more yellow with caustic, not pptd. by acids, sol. in conc. H,SO, (VR); a RED acid dye, fast 
to soap, alk., milling, washing and acids. 


501,118—July 11, 1893. M. Utricu and R. Laucu, Germany. (Bayer.) 
Blue-black tetrazo dye. (Process also claimed.) 


2-Tolidin coupled in HCl soln. with 1-NAPHTHYLMIN, again diazotized and coupled in alk. 
soln. with 2 mols. 8-dioxy NAPHTHALENE 4-sulfo. A gray black powd., sol. in aq. (BBr), 


94 DIGEST OF PATENTS 


nearly insol. in alc., sol. conc. H,SO, (GBk), pptd. on diln., aq. soln. not changed by. NERA 
redder with alk. carb., greener with NaOH, and pptd.; green sus to blue sLacx direct dye. 
S. 452—‘“Benzo Indigo Blue.” Note 476,337. 


501,160—July 11, 1803. W. PrirzincEerR, Germany. (Bayer.) 
Process of dyeing black. 

BENZIDIN or analogous diamin, coupled with 2 mols. 2-AMINO 8-NAPHTHOL 6-sulfo “G” or 
other similar disulfo acid, then applied to fiber, diazotized, and coupled with I-NAPHTHOL, 
PHENOL, or other. A BLUE, RED or violet BLACK developed dye. 

S. 319—‘‘Diamin Scarlet B.’’ 


501,500—July 18, 1983. I. Gans and M. Horrmann, Germany. (Cassella.) 
Black dye. 

BENzIDIN or other para diamin, coupled in alk. soln. with AMINO NAPHTHOL disulfo “H” 
and 2-AMINO 8-NAPHTHOL 6-sulfo “G,” also in alk. soln. Products are easily sol. in aq. (BBk), 
insol. in alc. and sol. in conc. H,SO, (B); BLacK or BLUE direct dyes that can be developed on 
fiber with phenols, amins, etc. 

S. 333—“‘Diamin Black BH.” Note 443,369 and 464,135. 


502,368—Aug. 1, 1893. R. Laucn and C. Krexeter, Germany. (Bayer.) 
Black azo dye. (Process also claimed.) 

4-Amino sALIcyLic acid coupled in acetic acid soln. with 1.8 dioxy NAPHTHALENE. <A green 
black powd., somewhat sol. in hot aq. (BR) soln. redder still with NH,, Na,CO, or NaOH, pptd. 
by mineral acids (R), slightly sol. ale. (V), sol. conc. H,SO, (GB), pptd. on diln. (YBr); 
a BLACK acid mordant (Cr) dye suitable for printing, fast to soap and alk. 

Note 502,369 and 509,623. 


502,369—Aug. 1, 1893. R. Laucu and C. KreKELER, Germany. (Bayer.) 
Reddish-blue azo dye. (Process also claimed.) 

4-Amino SALICYLIC acid coupled in dil. NaOH soln. with 2-NaPHTHOL carbo. A green 
black powd., sol. in aq. (BBr), not changed by alks., pptd. by acids, diff. sol. in alk. or alc. 
(VR), insol. dil. acids, sol. in conc. H,SO, (VR), not changed on diln.; a violet BLUE acid 
mordant dye for printing, fast to soap. 

Note 502,368. 


502,912—Aug. 8, 1803. A. F. Porrriter and D. A. RosENsTIEHL, France. 


Black azo dye. (Process also claimed.) 

1-NAPHTHYLAMIN disulfo, or any mono or disulfo amin coupled in HCl soln. with 1- 
NAPHTHYLAMIN and diphenyl 3-PHENYLENE DIAMIN or other di alkyl or aryl meta diamin. A 
dark powd., slightly sol. in aq.; a blue BLacK direct dye fast to soap, air, light, and adapted 


for printing. 
S. 267—“‘Anthracite Black B.” or “Phenylene Black.” 


503,148—Aug. 15, 1893. R. Laucu, Germany. (Bayer.) 
Substantive brown dye. (Process also claimed.) 

Brenzip1n coupled in Na,CO, soln., with saticytic acid and in same soln. with 1-NAPHTH- 
LAMIN, separated, sulfonated in fuming H,SO, (twenty per cent) at 30° again diazotized and 
coupled with 1-NAPHTHYLAMIN. A gray black powd., easily sol. in aq. (Br), diff. sol. in alc., 
sol. in alk., insol. in acids, sol. conc. H,SO, (V), on diln. paler and pptd. (Br); a BROWN 


direct dye. 
Near S. 447—‘‘Benzo Gray S.” .Note 476,393 (S. 447) which employs “NW” acid as 


third component. 


506,284—Oct. 10, 1893. M. Uxricn and J. BamMMANN, Germany. (Bayer.) 
Blue coloring-matter and process of making same. 

To.IpIN or dianisidin coupled in alk. soln. with 2 mols. 1-AMINO 8-NAPHTHOL 4-Sulfo. Pro- 
ducts are easily sol. in aq. (VB), insol. conc. Na,CO, or NaOH, sol. in conc. H,SO, (B), pptd. 
on diln. (B); a BLUE to green BLUE direct dye, fast to alk. and acid and can be diazotized and 


coupled on the fiber. 
S. 388—‘“‘Chicago Blue R.” Schulz credits this dye to Miller (1893). 


ee a 


GROUP VI.—AZO 95 


509,623—Nov. 28, 1893. R. Laucu, Germany. (Bayer.) 
Brown dye. (Process also claimed.) 


4-Amino SALICYLIC or similar aromatic amino hydroxy carbo acid, coupled in alk. soln. 
with RESORCIN or ORCINOL and treated with HNO, in HCl soln. to introduce nitrosyl. A dark 
brown paste somewhat sol. in hot aq. and alc. (Br) in conc. H,SO, (Br), pptd. partly on diln.; 
a BROWN direct or acid mordant dye (Fe Cr). 

Note 452,197 and 502,368. 


509,635—Nov. 28, 1893. M. Utricw and J. BAamMMANN, Germany. (Bayer.) 
Brown dye. (Process also claimed.) 


BeEnzip1n coupled in acetic soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo, then in neut. soln. 
with BISMARCK BROwN. A dark brown powd., easily sol. hot aq. (VBr) pptd. by HCl, sol. conc. 
H,SO, (VBk) pptd. on dil.; a BRown direct dye that can be diazotized on fiber and coupled with 
2-naphthol and is then fast to washing and soap. 


509,929—Dec. 5, 1893. M. MoeELuerR, Germany. (Berlin.) 
Blue azo dye. 


DIANISIDIN or other para diamin, coupled with 2 mols. 1-AMINoO 8-NAPHTHOL 4-sulfo, or 
with 1 mol of this and 1 mol. of a PHENOL, amin, amino phenol, sulfo or carbo acid. 
S. 388—“Chicago Blue R.”’ 


511,532—Dec. 26, 1893. R. Kotue, M. Utricw and O. Dresser, Germany. (Bayer.) 
Blue dye. (Process also claimed.) 


BENZIDIN or other para diamin, coupled in alk. carb. soln. with 2 mols. of 1-amino 8-NAPH- 
THOL 2.4-disulfo acid. A dark blue powd. easily sol. in cold aq. (GB), insol. in alc., in conc. 
H,SO, (G), on diln. (B); a green Biux direct dye, fast to alk. 

S. 424. “Chicago Blue 6B.’”’ Dye is credited by Schulz to Moller, 1894. 


511,688—Dec. 26, 1893. T. DiguHt, and M. Moetier, Germany. (Berlin.) 
Blue-black azo dye. 


4-PHENYLENE DIAMIN coupled in alk. soln. with 1-AmINo 8-NAPHTHOL 6-sulfo. Product is 
sol. in hot aq. (dark V), in alc. (B), in conc. H,SO, (GB), giving fine ppt. on diln. (V); a 
dark sLuxE direct dye. 

S. 245—“‘Kyanza Black B.’”’ Sulfo acid differs from Dahl’s gamma acid, 512,167. 


512,116—Jan. 2, 1804. R. KircuwHorr, Germany. (Berlin.) 
Crimson azo dye. (Process also claimed.) 


SuULFANILIC acid coupled in HCI soln. with 2-anisipIN, again diazotized and coupled in alk. 
soln. with 2-NAPHTHOL 8-sulfo. A red brown powd., easily sol. in aq. (R), more diff. sol. 
in alc., insol. in ether, sol. in conc. H,SO, (GB), pptg. free color acid on diln.; a violet RED 
acid or acid mordant (Al) dye. 

S. 259—‘‘Poncean 10RB.” 


512,167—Jan. 2, 1894. Theodor Dizut, Germany. (Berlin.) 
Blae-black dye. 


4-PHENYLENE DIAMIN azO I-NAPHTHYLAMIN Coupled with 2 mols. 4-AMINO NAPHTHOL sulfo, 
or naphthionic acid. Product is sol. in aq., sparingly sol. in alc., sol. in conc. H,SO, (B), pptd. 
on diln.; a blue srack direct dye, fast to acids, alk., air and light. 

S. 24s—“‘Nyanza Black B.” Note 491,410 and 511,688 for related dye. 


512,493—Jan. 9, 1804. M. Uuricu and J. BAmMmann, Germany. (Bayer.) 
Blue dye. (Process also claimed.) 

DIANISIDIN or other para diamin, coupled in acetic soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo, 
then with 2-NAPHTHOL or I-NAPHTHOL 5-sulfo or other. A dark blue powd., easily sol. in aq., 
almost insol. in hot alc., sol. in conc. H,SO, (G), pptd. on diln. (B); a BLUE direct dye, fast 
to acid and alk. 

Near S. 418—“Diamin Brill. Blue G.” 


514,599—Feb. 13, 1894. M. Horrmann and C. F. Daimuer, Germany. (Cassella.) 
Disazo dark-green dye. (Process also claimed.) 


4-NITRANILIN, or other amin, coupled in acid or neut. sol. with 1t-amino 8-NAPHTHOL 3.6- 
disulfo “‘H,” then in alk. soln. with tetrazo BENZIDIN or other tetrazo comp., and PHENOL or’ 


96 DIGEST OF PATENTS 


other aromatic oxy comp. or sulfo deriv. A dark green powd., easily sol. aq. (B or G), nearly 
insol. in alc., sol. conc. H,SO, (VBk), pptd. on diln. (Bk); a dark crEeEN acid or direct dye. 
S. 475—“‘Diamin Green G.” 


514,931—Feb. 20, 1894. M. HorrmMann and Carl Kroun, Germany. (Cassella.) 
Brown azo dye. (Process also claimed.) 


BenzipIN or other para diamin coupled with 1 mol. each of saricyniic acid and 1-amino 
8-NAPHTHOL 3.6-disulfo then coupled in alk. soln. with 3-PHENYLENE DIAMIN, or other. Other 
aryl oxy carbo acids are claimed. Amino SALIcyLIc acid or other amin used with 2 mols. third 
component gives tetrakis azo dye. Fast yellow BRown direct dyes. 

S. 448—“‘Diamin Bronze G.” 


515,100—Feb. 20, 1894. A. WEINBERG, Germany. (Cassella.) 
Basic yellow dye. (Process also claimed.) 


4-Nitro BENzyL chloride condensed with pIMETHYLAMIN, the HCl] salt reduced, diazotized 
and coupled with rEsorcIN, or other. Or nitration may take place after condensing benzyl 
chloride and the amin. Other benzyl alkyl amins claimed. Inventor claims basic dye the salts 
of which are same shade, because basic substitution is in side chain, whereas salts of basic azo 
dyes substituted in nucleus differ in color from dye proper. YELLOW to BROWN basic mordant 
dyes. 

S. 75—‘‘New Phosphin G.” 


515,339—Feb. 27, 1894. A. IsraEL and K. Patust, Germany. (Bayer.) 
Gray dye. (Process also claimed.) 


Dehydro thio ToLtuipIn sulfo coupled with 1-NAPHTHYLAMIN, again diazotized and coupled 
with 1.8-dioxy NAPHTHALENE 4-Sulfo or “S” acid. Blue-cray to gray-BLAcK direct dye, fast to 
alk., acid. 


515,381—Feb. 27, 18094. M. Uturicu, J. BAMMANN and M. Herzperc, Germany. (Bayer.) 
Brown dye. (Process also claimed.) 


BENzIDIN coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo, then in acid soln. with 3-PHENYLENE 
DIAMIN, finally combined in alk. carb. soln. with diazo 1-NAPHTHYLAMIN and temp. raised to 100°. 
A direct BROwN and developed dye, when coupled in fiber with 2-naphthol is fast to washing, 
soaping. 

Near S. 462—‘“‘Erie Direct Black GX.” 


515,764—Mar. 6, 1894. Arthur G. Green, England. (Brooke.) 
Red azo dye. (Process also claimed.) 


AZOXY 2-TOLUIDIN, or other aromatic azoxy or amino azo comp., coupled in acetic soln. with 


I-NAPHTHOL 4-sulfo, then in alk. carb. soln. with 2-NAPHTHOL. See long list of other com- 
ponents. Rep acid dye, fast to milling, scouring, acids and alks. 


515,897—Mar. 6, 18094. J. J. Brack, Switzerland. (Durand.) 
Polyazo dye. (Process also claimed.) 

ToLIDIN, or other para diamin, coupled with saticy1Lic acid and 2 mols. of this diazo product 
coupled with dioxy DIPHENYL METHANE (FORMALDEHYDE condensed with 2 mols. PHENOL by means 
of HCl). A direct yELLow dye for cotton. 


516,203—Mar. 3, 1804. M. HorrMann and C, Kroun, Germany. (Cassella.) 
Gray azo dye. (Process also claimed.) 


BENZIDIN or other para diamin coupled with 2 mols. 1-AMINO 8-NAPHTHOL 3.6-disulfo, then 
tetrazotized and coupled in alk. soln. with 2 mols. 3-PHENYLENE DIAMIN or other amin or phenol. 
Blackish gray powd., sol. in aq. (Gy), insol. in alc., sol. in conc. H,SO, (B), ppts. on diln. 
(Bk); a direct Gray dye. The second coupling reaction can take place on fiber. 

Near S. 491—‘“‘Dianil Black PR.” 


516,380—Mar. 13, 1894. C. RupotpxH, Germany. (Oehler.) 
Brown azo dye. (Process also claimed.) 

2.4-TOLUYLENE DIAMIN 6-sulfo coupled with 3-PHENYLENE DIAMIN. Blackish powd., insol. 
in alc., sol. in aq. (Br), sol. in conc. H,SO, (dull V), ppts. with HCl (BkBr); a direct BROWN 
dye fast to soap. 

S. 285—“‘Toluylen Brown G.” ‘The formula in Schulz gives an internal disazo coupling 
which is unusual. See also 516,381. 


Ps See ee 


GROUP VI.—AZO 97 


516,381—Mar. 13, 1804. C. Rupotpu, Germany. (Oehler.) 
Azo dye from amidophenolsulfo-acid. (Process also claimed.) 


ToLipIn coupled with amino PHENOL sulfo (from METANILIC acid, sulfonated and fused in 
alkali), then with REsorcIN and finally with diazo NAPHTHIONIC acid. Greenish black powd., sol. 
in ag. (RBr), sol. in H,SO, (V), with NaOH (VR), and with HCl (Br.) ppt.; a direct RED 
dye. 

S. 381—‘‘Azo Corinth” 


516,468—Mar. 13, 1804. J. J. Brack, Switzerland.. (Durand.) 
Yellow tetrazo dye. (Process also claimed.) 


DiIBENZIDIN methane, obtained by condensation of 2 mols. BENzIDIN or other para diamin 
with FORMALDEHYDE, coupled with 2 mols. saLicyLic acid or other carbo acid. Brownish powd., 
sol. in aq., sol. in conc. H,SO, (RBr); a direct yELLow dye. 


516,604—Mar. 13, 1804. R. Krrcunorr, Germany. (Berlin.) 
Black dye. (Process also claimed.) 


2-TOLIDIN or other para diamin coupled with 2-AMINO 8-NAPHTHOL 3.6-disulfo. again diazo- 
tized and coupled with 2 mols. 3-TOLUYLENE DIAMIN, resorcin or other meta derivs. Products 
are sol. in aq. (BrV), diff. sol. in alc., insol. in ether, with conc. NaOH ppt. (BrBK); direct 
BLACK dyes, fast to acids and alks. 

S. 452—‘“‘Columbia Black R.” 


516,756—Mar. 20. 1894. J. J. Bracx, Switzerland. (Durand.) 
Red tetrazo dye. (Process also claimed.) 


as-DIAMINO base, formed by condensation of ToL_ipIN or other para diamin and aniLIn HCl 
or other mono amino comp. with FORMALDEHYDE, tetrazotized and coupled with 2 mols. NAPHTH- 
Ionic acid, or derivs. Red-brown powd., sol in aq. (Rt), sol. in alc., sol. in conc. FSO. CV); 
a direct RED dye. 


516,757—Mar. 20, 1804. J. J. Bracx, Switzerland. (Durand.) 
Blue tetrazo dye. (Process also claimed.) 


FORMALDEHYDE, DIANISIDIN and ANILIN HCl, 2-amino phenol or other mono amino base 
condensed to diamino base then coupled with 2 mols. 1-NAPHTHOL 4- or 5-sulfo or other naphthol 
sulfo acid. Brown powd., sol. in aq., diff. sol. in alc., sol. conc. H,SO,; a direct BLuE dye. 

Note 516,758, -59, and -60, also 519,522-23. 


516,758—Mar. 20, 1894. J. J. Bracx, Switzerland. (Durand.) 
Blue tetrazo dye. (Process also claimed.) 

FoRMALDEHYDE, TOLIDIN and tolidin HCl, or 3-phenylene diamin, condensed to diamino 
compound, then coupled with 2 mols. 1-NAPHTHOL 4-sulfo or other alfa naphthol alfa sulfo 
acid, or para diamins. Brown powd., sol. in aq. (Bt), diff. sol. alc., sol. conc. H,SO, (B); a 
direct VIOLET dye. 


516,759—Mar. 20, 1804. J. J. Bracx, Switzerland. (Durand.) 
Red tetrazo dye. (Process also claimed.) 

FoRMALDEHYDE, TOLIDIN and tolidin HCl or phenylene diamin condensed to diamin then 
coupled with 2 mols. NAPHTHIONIC acid or other naphthylamin sulfo acids, para diamins or 
aromatic diamins. A red powd., sol. in conc. H,SO, (GyB); a direct RED dye. 


516,760—Mar. 20, 1894. J. J. Bracx, Switzerland. (Durand.) 
Blue tetrazo dye. (Process also claimed.) 

FoRMALDEHYDE, DIANISIDIN and dianisidin HCl, or 3- or 4-phenylene diamin, condensed, 
diazotized and coupled with 1-NAPHTHOL 4-sulfo or other naphthol sulfo acids, or aromatic 
diamins. A brown powd., sol. in aq., diff. sol. in alc., sol. in conc. H,SO, (B); a BLUE and 
blue vioter direct dye. 

Note 516,757. 


517,533—Apr. 3, 1894. A. WEINBERG, Germany. (Cassella.) 
Process of dyeing by the aid of paramidodiphenylamin, 

DIAMIN BLACK BLUE E or other amino azo compound, especially disazo, diazotized on fiber 
and combined with 4-amino DIPHENYLAMIN. VARI-COLORED developed dyes, fast to washing and. 
light. 


98 DIGEST OF PATENTS 


519,522—May 8, 18094. J. J. Brack, Switzerland. (Durand.) 
Polyazo yellow dye. (Process also claimed.) 

FoRMALDEHYDE and PHENOL condensed, then coupled with tetrazotized sBENzipIN, tolidin 
or other diamin which has previously been coupled with one equivalent of suLFaNniLic acid, 
anilin, other amin or their sulfo acids. A brown powd. sol. in aq., sol. in H,SO, (RV); a direct 
YELLOW to yellow RED dye. 


519,523—May 8, 1894. J. J. Brack, Switzerland. (Durand.) 
Polyazo yellow dye. (Process also claimed.) 

FoRMALDEHYDE condensed with PHENOL then coupled with tetrazotized TOLIDIN, benzidin, 
etc. which has previously been combined with one equivalent of NAPH?THIONIC acid or other 
amin, diamin, or derivs. A brown powd., sol. in aq., sol. in H,SO, (B); a YELLOW, ORANGE, or 
RED direct dye. 

Addition to 516,757. 


521,095—June 5, 1894. H. A. Berntusen and P. Junius, Germany. (Badische.) 
Substantive blue dye. 

To.ipIN coupled with 2-amino 5-NAPHTHOL 7-sulfo and NAPHTHIONIC acid. The product is 
sol. in aq. (RV), diff. sol. in alc., insol. in benzene, ether and ligroin, sol. in H,SO, (B); direct 
BLUE dye fast to acids, alk. and light, and can be diazotized on fiber and coupled with oxy 


amino or other comps. to form very fast colors. 
S. 385—‘‘Oxamin Blue 4 R.” 


521,096—June 5, 1894. H. A. Berntusen and P. Junius, Germany. (Badische.) 
Substantive violet dye. 

BENZIDIN coupled with 2 mols. 2-AMINO 5-NAPHTHOL 7-sulfo. Dark powd., sol. in aq. (R), 
slightly sol. in alc., insol. in benzene, ether and ligroin, sol. in H,SO, (B), diazotized on fiber 


(GyG); a direct vioLET and gray GREEN dye, fast to acids, alk., light and can be diazotized on 
fiber. 


521,985—June 26, 1894. M. Moe.ier, Germany. (Berlin.) 
Blue dye. 

2-TOLIDIN coupled with 2 mols. I1-AMINO 2-NAPHTHOL 3.6-disulfo made as described in Ser. 
- 466,691 from I-NAPHTHYLAMIN 3.6-disulfo sulfonated to trisulfo then fused in alk. to form 
naphthol. Other combinations claimed. Product sol. in aq., nearly insol. in alc., sol. in conc. 
H,SO, (B), on diln. (VB) and ppts. (B); a sLur direct and acid dye. 

S. 391—“‘Diamin Blue 3B.’’ Schulz credits this dye to Bammann and Ulrich, 1890. Note 
521,986. 


521,986—June 26, 1894. M. MorE.uEr, Germany. (Berlin.) 
Blue dye. 


DIANISIDIN coupled with 2 mols. 1-AMINO 8-NAPHTHOL 3.6-disulfo or 1 mol. of this, and 
1 mol. of phenol, amin or sulfo or carbo acids. The product is sol. in aq., insol. in alc., sol. 
in H,SO, (VB), ppts. on diln. with aq. (B); a green sur direct and acid dye. 

S. 426—‘“‘Diamin Pure Blue.’ This dye also is credited to Bammann. 


524,005—Aug. 7, 1804. M. Uuricu and J. Bammann, Germany. (Bayer.) 
Azo dye. (Process also claimed.) 


Dehydro thio ToLuIpIN or homolog, coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo, ethyl 
ester. A brown red powd., sol. in aq. (VR), sol. in alc. (R), sol.. in conc. H,SO, (B), pptd. 
on diln. (R); a violet RED direct dye. ; 


524,069—Aug. 7, 1894. M. Uuricu and J. BammMann, Germany. (Bayer.) 
Blue tetrazo dye. (Process also claimed.) 

Drantsip1n, homolog or deriv. coupled with 1.7-diozy NAPHTHALENE 4-sulfo and 2-NAPHTHOL 
3.6-disulfo, or other. A brown powd., sol. in aq. and conc. H,SO, (B); a fast green BLUE 
direct dye. : 

S. 413—‘Direct Violet BB.” $. 414—‘Indazurin B.” 


GROUP VI.—AZO 99 


524,070—Aug. 7, 1894. C. O. Mutuer, Switzerland. (Basle.) 
Blue tetrazo dye. (Process also claimed.) 

DIANISIDIN,. or other para diamin, coupled with 1.7-dioxy 4-sulfo 2-NaPpH?THOIC acid then 
with a second mol. of same, or other component (see list). A brown powd., sol. in aq. (B), 
sol. in H,SO, (GB); a direct sLug dye. 

S. 396—“Indazurin R N,” also 399, 427, 429 and 430. 


524,220—Aug. 7, 1894. - C. Scurause, Germany. (Badische.) 
Substantive blue dye. (Process also claimed.) 

BENZIDIN 3.3’-dicarbo acid coupled with 2 mols. benzoyl 1-AMINO 8-NAPHTHOL 4-sulfo. Identity 
test for dye is made by fusing in. NaOH to split off benzol and extracting benzoic acid from 
acidified soln. with ether. The product is sol. in aq,. insol. in alce., ether or benzene; a direct 
BLUE dye. 


524,251—Aug. 7, 18094. P. Juuius, Germany. (Badische.) 
Soluble safranin azo naphthol. 

SAFRANIN T. obtained by oxidation of ToLUYLENE DIAMIN, 2-TOLUIDIN and ANILIN, or other, 
diazotized and coupled with 1-NapHTHoL and a soluble salt of resulting base formed by com- 
bining with acids, preferablly HCl or acetic. A dark powd., insol. in alks., sol. in alc., dif. 
sol. in benzene, sol. in H,SO, (Br.); a BLuEg basic mordant dye, suitable for lakes on tanno- 
metallic mordant. 

S. 126—“Indoin Blue R.” Schulz reports use of 2-NAPH?THOL instead of 1-naphthol. 


524,252—Aug. 7, 1894. P. Jutius, Germany. (Badische.) 
Dimethyl safranin azo naphthol. 

Dimethyl saFRANIN, coupled with 2-NapHTHOL, then rendered sol. in aq. by forming salt 
with acids. A dark powd. insol. in alks., sol. in alc., very dif. sol. in benzene, sol. in H,SO, 
(G); a BLUE basic mordant dye, suitable for lakes on tanno-metallic mordant. 

S. 126—“Indoin Blue R.” Addition to 524,251. This patent gives specific claims, for 
generic claims see 524,254. 


§24,253—Aug. 7, 1804. P. Junius, Germany. (Badische.) 
Safranin azo naphthol dye. 

Dimethyl sarranin, coupled with 1-NAPHTHOL, then rendered sol. in aq. by combination 
with acids. Dark powd., sol. in aq., insol. in alks., very dif. sol. in benzene, sol. in alc., sol. in 
H,SO, (Y); a BiuE basic mordant dye, suitable for lakes on tanno-metallic mordant. 

Addition to 524,251. For generic claims see 524,254. 


§24,254—Aug. 7, 1804. P. Junius, Germany. (Badische.) 
Safranin azo naphthol lake. (Process also claimed.) 

SAFRANIN or derivs. coupled with 1- or 2-NAPHTHOL, adding sufficient acid to render sol. 
in aq. Lake is formed by tannin and tartar emetic or dye is fixed on fiber by treatment first 
with sumac, Sb.or Fe salt, and aluminum sulfate, then passing through dye soln. Prod. is 
sol. in aq. and in H,SO, (G); a Brug basic mordant dye for lakes, nearly as fast as indigo 
when mordanted. 

Addition to 524,251. Detailed tests for identification of comps. are given. 


524,261—Aug. 7, 1894. C. I. Mutxiuser, Germany. (Badische.) 
Orange diazo dye. ‘ 

PrimMuLiIn coupled with 3-PHENYLENE DIAMIN disulfo then combined with diazo SULFANILIC 
or metanilic acid. A direct oRANGE dye. 

S. 210—“Cotton Orange R.”? Note 524,262. 


524,262—Aug. 7, 1804. C. L. Miuier, Germany. (Badische.) 
Orange dye. (Process also claimed.) 

PrimMuLin coupled with 3-PHENYLENE DIAMIN disulfo. An orange-yELLOw direct dye. 

S. 192—“Cotton Orange G.” 


524,665—Aug. 14, 1894. C. BitLow, Germany. (Badische.) 
Black disazso dye. : 

I-AMINO 8-NAPHTHOL sulfo combined in acetic soln. with diazo suLFANILIC acid then in alk. 
soln. with diazo anrLIn. Other components and different order in coupling claimed. A direct 
BLACK dye. 


100 DIGEST OF PATENTS 


525,245—Aug. 28, 1804. A. WEINBERG, Germany. (Cassella.) 
Black azo dye. (Process also claimed.) ; 

Diamino DIPHENYLAMIN coupled in alk. soln. with 1 mol. each of 2-AMINO 8-NAPHTHOL 6- 
sulfo “‘Gamma” and 3-PHENYLENE DIAMIN. Prod. may be rediazotized and coupled with two 
mols. of third component. A Brack direct and developed (CrO,) dye. 

Near S. 295—‘“‘Diphenyl Fast Black’ and derivs. 


§25,492—Sept. 4, 1804. C. Dursperc, Germany. (Bayer.) 
Blue dye. (Process also claimed.) 

DIANISIDIN coupled with 2 mols. 2-NAPHTHOL. Process for printing given in detail. A BLUE 
direct and developed dye, suitable for printing. 

S. 408—‘“Dianisidin Blue.’’ Patent is credited by Schulz to Storck (1893). Note 569,392 
and 575,228. 


525,626—Sept. 4, 1894. A. ScuMip, Switzerland. (Basle.) 
Blue-black disazo dye. 

BENzIDIN, or other, coupled in alk. soln. with 1 mol. each of sulfo dioxy NAPHTHOIC acid and 
2-AMINO 8-NAPHTHOL 6-sulfo or other. A blue-sLrack direct or developed dye, that can be 
developed on fibers by pyrolignite of Fe or coupled. 

Near S. 353—‘“‘Direct Indigo Blue SN” and S. 354—‘“Direct Gray R.”’ 


525,656—Sept. 4, 1804. P. Junius, Germany. (Badische.) 
Azo dye. 


2.4-DINITRANILIN coupled with diethyl mreranizic acid, or other. A vio.ET acid dye. 
S. 59>—“‘Wool Violet S.’’ 


525,657—Sept. 4, 1894. P. Jurius, Germany. (Badische.) 
Azo dye. 

4-NITRANILIN coupled with dimethyl mxEraniiic acid, or diethyl comp. <A Rep acid dye, fast 
to acids, light, washing and equalizes well. 


526,763—Oct. 2, 18094. A. WEINBERG, Germany. (Cassella.) 
Black azo dye. (Process also claimed.) 

Acet 4-PHENYLENE DIAMIN coupled with alk. soln. with 2-aAm1no 8-NAPHTHOL  6-sulfo, 
saponified, tetrazotized and coupled with 2 mols. 3-PHENYLENE DIAMIN, or one mol. each of two 
components and if desired again diazotized and coupled. A direct BLacKk dye, fast. 

Near S. 436—‘“‘Columbia Black FB.”? Note 454,645. 


528,965—Nov. 13, 1804. F. Mun ert, Hungary. (Kinzleberger.) 
Manufacture of yellow and orange dye. (Product also claimed.) 

3- OF 4-NITRANILIN coupled in acetic soln. with 1.2.4-RESORCYLIC acid; a YELLOW Or ORANGE 
acid mordant (Cr, Al) dye, fast to washing and light. 

S. 491—“‘Prager Alizarin Yellow G.” 


5631,149—Dec. 18, 1894. J. J. Brack, Switzerland. (Durand.) 


Substantive red dye. (Process also claimed.) 
Amino p1IToLIpIN methane (from tolidin and formaldehyde, see Intermediates) coupled with 


3 mols. NAPHTHIONIC acid, or other. 
Addition to 616,756. 


532,125—Jan. 8, 1895. A. WEINBERG, Germany. (Cassella.) 


Blue disazo dye. (Process also claimed.) 
Dranisip1n coupled with 1-chlor 8-NAPHTHOL 3.6-diulfo then with 1 mol. of same, of 


NAPHTHIONIC acid, or other. A BLUE direct dye. 
S. 418—“Diamin Brill. Blue G.” Note also 464,135 and 535,037. 


532,479—Jan. 15, 1895. Re. 11,491—Apr. 30, 1895. 
K. Patux and O. Dressrt, Germany. (Bayer.) 
Red dye. (Process also claimed.) 
Dehydro thio TroLurmpIN, or the 3-xylidin or ps-cumidin comp., coupled in alk. or acid soln. 
with 2-AMINO 5-NAPHTHOL 1.7-disulfo and heated to 90° to complete reaction. A RED direct dye, 
fast to alk. and acid, can be coupled on fiber, then is fast to soaping, milling. 


GROUP VI.—AZO IOI 


533,463—Feb. 5, 1805. M. Horrmann, Germany. (Cassella.) 
Black azo dye. (Process also claimed.) 


Acet 1.4-NAPHTHALENE DIAMIN 6- or 7-sulfo coupled with 1-NAPHTHYLAMIN. then diazotized 
and coupled with 2-amINo 8-NAPHTHOL 6-sulfo or other, finally saponified. A BLACK direct dye. 
S. 274—“‘Diaminogen B.” Note 560,796. 


533,508—Feb. 5, 1805. M. Uxricnu and J. BAMMann, Germany. (Bayer.) 
Blue dye. (Process also claimed.) 


BENzIDIN coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo “H’’ then with 1-AMINO 8-NAPHTHOL 
4-sulfo “S.” A sBLuE and BLAcK direct dye, fast to alk. and acid. Can be diazotized on fiber 
and coupled with naphthols. 

S. 336—“Benzocyanin R,” S. 390 and 425. Note 578,422. 


534,573—Feb. 19, 1805. R. PacGanini. (Basle.) 
Blue disazo dye. (Process also claimed.) 


ToLIDIN, or dianisidin, coupled in alk. soln. with 1 mol. each 1-oxy NAPHTHOIC disulfo then 1- 
NAPHTHOL 4-sulfo. A BLUE to VIOLET direct dye. 


535,036—Mar. 5, 1895. A. WEINBERG, Germany. (Cassella.) 
Brown dye. (Process also claimed.) 

BENzIDIN, or other, coupled with saticyztic acid then with phenyl 2-AMINO 8-NAPHTHOI. 
6-sulfo, formed by phenylating 2-amino 8-naphthol 6-sulfo. 

Near S. 344—“‘Diamin Brown N.” 


535,037—Mar. 5, 1805. A. WEINBERG, Germany. (Cassella.) 
Bluish-red azo dye. 

Dehydro thio 4-roLuipIN, or other, coupled with 1-chlor 8-NAPHTHOL 3.6-disulfo. A violet- 
RED direct dye, fast to light, mineral acids, etc. 

_$. 119>—“‘Diamin Rose R,” S. 418—‘“‘Brill Blue C.”? Addition to 592,125. 


536,431—Mar. 26, 1805. M. Kaun and F. Runxet, Germany. (Bayer.) 
Black dye. (Process also claimed.) 


4.4’-Diamino DIPHENYLAMIN 2’-sulfo coupled in alk. soln. with 2-AMINO 8-NAPHTHOL 6-sulfo 
“G,” tetrazotized and coupled with 2 mols. 3-PHENYLENE DIAMIN, or other. A BLACK direct dye, 
fast to acids, alks. 


536,532—Mar. 26, 1895. R. KircuHHorr, Germany. (Derlin.) 
Blue azo dye. 


4-NITRANILIN coupled with 2-amino 4-crRESOL, methyl ether, (OH=1), reduced with alk. 
sulfid, tetrazotized and coupled in alk. soln. with 2 mols. 2-AMINO 8-NAPHTHOL 6-sulfo ‘‘Gamma.” 
A BLUE to BLACK direct and developed dye, can be coupled on fiber to deeper and faster shades. 


536,878—Apr. 2, 1895. R. KircHuoFFr, Germany. (Berlin.) 
Black dye. 


4-NITRANILIN coupled with 2-amino 4-cRESOL, methyl ether, reduced to diamino comp. by alk. 
sulfids, tetrazotized and coupled with saLticy1ic acid, and 2-AMINO 8-NAPHTHOL 6-sulfo. 
S. 353—‘‘Direct Indigo Blue BN” and S. 439—‘‘Direct Indigo Blue A.’’ Note 536,879-80. 
Schulz gives above pat. under S. 353, but there is no apparent connection, one being a tris-, 
the other a disazo dye. See 557,438 for same Schulz number. 


536,879—Apr. 2, 1895. R. Kircuuorr, Germany. (Berlin.) 
Blue-black dye. 


4-NITRANILIN coupled with 2-amino 4-crEsoL, methyl ether (OH=1) reduced then tetrazotized 
and coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo and 2-AMINO 8-NAPHTHOL 6-sulfo “G.” A 
BLACK to violet GRAY direct and developed dye, can be developed on fiber. 

Note 536,880 and 536,878. 


536,880—Apr. 2, 1895. R. KircHuorr, Germany. (Berlin.) 
Blue dye. 

4-NITRANILIN coupled with 2-AMINO 4-CRESOL, methyl ether, (OH=1) reduced then 
tetrazotized and coupled with 2 mols. of 2-AMINO 8-NAPHTHOL 6-sulfo. 

Note 536,878 and 536,879. 


102 DIGEST OF PATENTS 


539,699—May 21, 1805. M. MoeE.ier, Germany. (Berlin.) 
Blue dye. (Process also claimed.) 
BENzIDIN coupled in alk. soln. with 2 mols. 1-aMINO 8-NAPHTHOL 2.4-disulfo or with 1 mol.. 


each of this and of a phenol, amin, sulfo or carbo acid. A sBiug direct and acid dye. 
Note Ser. 466,691 for original claim. 


541,750—June 25, 1895. W. Herzperc and O. Weser, Germany. (Berlin.) 
Black dye. 


I-AMINO 8-NAPHTHOL 3.6-disulfo disazo di-anin1In coupled in alk. soln. with 2 mols. 3- 
TOLUYLENE DIAMIN, or Other. 


541,859—July 2, 18905. R. Korerr, Hungary. (Kinzlberger.) 
New amido base and colors therefrom. (Process also claimed.) 

2.2/-TOLIDIN, 2.2/-dianisidin, 1-naphthylamin, 2-toluidin or other primary amin or diamin 
condensed with FORMALDEHYDE in conc. H,SO, to form new base with amino groups intact. 
Products are non cryst., (m.p.'60°), sol. in ether, with acids give ppts. (white), readily form 


diazo to tetrazo comps. to give VARI-COLORED acid and direct dyes. 
Note 542,073 (Brack). Dyes are not claimed except in title of patent. 


542,022—July 2, 18095. EK. Lauser and L. Caserti, Italy. (Bayer.) 
Process of dyeing. (Product also claimed.) 

Any antimonious salt, such as the double fluoride (SbF,NaF) is pptd., with sufficient alk. 
carb. as Sb (OH),,* the latter mixed with glycerin or other diluent, then with the Na salt of 
2-NAPHTHOL and with dil. NaOH to a thick liquid which is applied to the fiber, and a diazo 
comp. is allowed to react upon the fiber. Vari-coLorED developed dyes are produced. 

*Antimonious oxide preserves the 2-naphthol from decomposition for a long time. 


§42,073—July 2, 1895. J. J. Brack, Switzerland. (Durand.) 
Substantive cotton dye. (Process also claimed.) 
Base derived from DIANISIDIN and FORMALDEHYDE coupled in alk. soln. with 2 mols. 1- 


AMINO 8-NAPHTHOL 3.6-disulfo or other. A GRAy to BLACK direct dye. 
Note 541,859 for comp. condensed differently (Koreff). 


543,212—July 23, 1895. R. Korerr, Hungary. 
Azo dye. (Process also claimed.) 
Tetra amino DITOLIDINO methane, obtained by condensing 2-tolidin and formaldehyde, 


coupled with 4 mols. NAPHTHIONIC acid, or other. A RED, VIOLET or BLACK direct dye. 
Differences from Brack condensation noted. 


543,539—July 30, 1805. K. Patrue and A. IsragL, Germany. (Bayer.) 
Brown azo dye. (Process also claimed.) 


Dehydro thio totumpin sulfo coupled in acetic soln. with I-NAPHTHYLAMIN 6-sulfo, 
separated, re-diazotized and coupled with PHENOL, and purified product alkylated by heating 
in alk. fifty per cent alcohol at 100° in closed vessel with EtHyL bromide. Other components 
claimed. A yellow-Brown direct dye, fast to light, alk., and acid. 


543,747—July 30, 1895. M. Moe.ier and Carl OE£LscHLAEGEL, Germany. (Berlin.) 


Black azo dye. 

I-NAPHTHYLAMIN coupled in alk. soln. with 1-AmINo 8-NAPHTHOL 4-sulfo acid No. II, 
made acid with acetic and combined with diazo sunFANILIc acid. A BLAcK acid dye. 

Note isomeric dye from 1.8.5-acid (acid No. I) in 324,665. (Biilow). See also 543,748. 


543,748—July 30, 1895. M. Moexi.er and Carl OriscHLarceL, Germany. (Berlin.) 


Black azo dye. r 
I-NAPHTHYLAMIN coupled in alk. soln. with 1-AmiINo 8-NAPHTHOL 4-sulfo then combined in 
acetic soln. with diazo I-NAPHTHYLAMIN and with diazo sULFANILIC acid, one mol. each. The 
first coupling may also be in acid soln. A BLacxk direct dye. 
Addition to 543,747. 


Ay 


GROUP VI.—AZO 103 


544,699—Aug. 20, 1805. M. Uxricu and J. BamMmMann, Germany. (Bayer.) 
Blue dye and process of making same. 


Benzipin coupled in alk. soln. with 2 mols. 1-AMINO 8-NAPHTHOL 3.6-disulfo. A BLUE 
direct dye, fast to alks. 
S. 337—‘‘Diamin Blue BB.” Note 544,700. 


544,700—Aug. 20, 1895. M. Uxricu and J. BammMann, Germany. (Bayer.) 
Blue dye and process of making same. 


ToLipIn, coupled in alk. soln. with 2 mols. 1-AMINO 8-NAPHTHOL 3.6-disulfo. A BLUE 
direct dye, fast to alk. 
Near S. 337—‘‘Diamin Blue BB.’ Addition to 544,699. 


545,333—Aug. 27, 1895. H. A. BERNTHSEN, and P. Juzius, Germany. (Badische.) 
Azo orange dye. 


BENzIDIN disulfo, tetrazotized and coupled with 2 mols. of nitro 3-PHENYLENE DIAMIN, OF 
other. An ORANGE, direct dye, fast to acids, washing, and light. 
S. 360—‘‘Pyramin Orange R.” 


546,068—Sept. 10, 1895. F. Krecxe and I. Rosenserc, Germany. (Kalle.) 
Blue-black disazo dye. (Process also claimed.) 


I-NAPHTHYLAMIN 3.6-disulfo coupled in alk. soln. with 1-NAPHTHYLAMIN 7-sulfo, rediazotized 
and coupled with 2-NAPHTHOL 3.6-disulfo. Other components claimed. A VIOLET, BLUE, to 
BLACK acid dye. 

S. 273—‘“‘Biebrich Patent Black 4 AN” etc. Note 546,069 and -7o. 


546,069—Sept. 10, 1895. F. Krecke and I. Rosenserc, Germany. (Kalle.) 
Blue-black disazo dye. 


I-NAPHTHYLAMIN 3.6-disulfo coupled in alk. soln. with 1-NAPHTHYLAMIN 7-sulfo obtained 
by nitration and reduction of NAPHTHALENE 7-sulfo, rediazotized and coupled with 1-NAPHTHY- 
LAMIN. A blue BLAcK acid dye. 

S. 278—“Biebrich Patent Black.” Addition to 546,068. 


546,070—Sept. 10, 1895. F. Krecxe and I. Rosensperc, Germany. (Kalle.) 


‘Blue-black dye. 


Amino SALICyLIc acid coupled in alk. soln. with 1-NAPHTHYLAMIN 7-sulfo, rediazotized and 
coupled with 2-NAPHTHOL 3.6-disulfo. A blue BLacK acid mordant dye, fast to milling and 
light. 

S: 278—‘“‘Biebrich Patent Black.” Addition to 546,068. 


548,416—Oct. 22, 1805. A. AsHwortH and J. Burcer, England. 
Brown dye. (Process also claimed.) 

I- Of 2-NAPHTHYLAMIN coupled in alk. carb. soln. with nitroso NAPHTHOL bisulfite comp. 
A Brown acid mordant (Cr) dye, suitable for printing. 


548,460—Oct. 22, 18905. C. Ris, Switzerland. (Geigy.) 
Brown dye and process of making same. 

4-Amino PHENOL or sulfo acids, coupled with PyRoGALLIc acid in alk. carb. soln. A BROWN 
acid mordant (Cr) dye, suitable for printing. 

S. 84—‘‘Azochromin” and S. 138—‘‘Chrome Brown RR.” 


555,359—Feb. 25, 1806. H. A. BeRNTHSEN, and Paul Junius, Germany. (Badische.) 
Red dye and process of making same. 

Brenzip1n coupled with 1 mol. each of saticyLtic acid and 2-AMINO 5-NAPHTHOL 7-sulfo. 
When diazotized on fiber dyeing turns black and couples to dark shade. <A rep direct dye, and 


BLACK developed (coupled) dye. 
S. 346—“Oxamin Red.” Note 521,095 and -96. 


555,658—Mar. 3, 1806. R. Nrerzx1, Switzerland. (Hdéchst.) 
Yellow coloring-matter. (Process also claimed.) 
2-NAPHTHYLAMIN 8-sulfo coupled with saticyLic acid. A yrELLow (Al) and olive-YELLow 


(Cr) mordant dye, fast to milling on Cr mordant. 
Near S. 177—‘‘Chrome Yellow D.” 


104 DIGEST OF PATENTS 


556,164—Mar. 10, 1806. C. Ris and C. Simon, Switzerland. (Geigy.) 
Gray dye and process of making same. 
BENzIDIN coupled with 2 mols. dialkyl 2-amino 8-NAPHTHOL 6-sulfo or with 1 mol. of this 


and 1 mol. of 2-AMINO 8-NAPHTHOL 3.6-disulfo. A blue GRAY to BLACK direct dye, fast. 
S. 336—‘‘Diphenyl Blue Black.’”’ Note 567,413. 


556,298—Mar. 10, 18096. J. BaAmmMann and M. Uxricu, Germany. (Bayer.) 
Blue dye. (Process also claimed.) 

2-TOLIDIN, or other, coupled in alk. or acetic acid soln. with 1 mol. each of 1-AMINO 8- 
NAPHTHOL 3.6-disulfo “H’’* and dioxy NAPHTHALENE, or other. The order of coupling may be 
reversed. A BLUE to BLACK direct and developed dye, can be coupled on fiber to form blue- 
black shade. 

*For other pats. employing this acid see 498,873, 499,198, 544,699, and 544,700. 


557,435—Mar. 31, 18096. J. Scumip, Switzerland. (Basle.) 
Blue dye. 

BeEnzip1In, 2 mols., or other, coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo, or 1.8-dioxy 
naphthalene 3.6-disulfo, and free diazo group coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo, 
2 mols., or zt mol. each of two components. A BLUE to BLACK direct dye that can be 
diazotized on fiber, coupled with phenols, etc. 

Note 557,436, 557,439 and related pats. 557,437, 38, and 4o. 


557,436—Mar. 31, 18096. J. Scumip, Switzerland. (Basle.) 
Blue dye. 

BENzIDIN, 2 mols., coupled with 1 mol. r-amMiNno 8-NAPHTHOL 3.6-disulfo further diazotized 
and coupled with 1-NAPHTHOL 4-sulfo, 2 mols., (or 1 mol. of this and 1 mol. of another com- 
ponent). A BLUE to vIOLET direct dye. 

Addition to 557,425. 


557,437—Mar. 31, 1896. J. Scumip, Switzerland. (Basle.) 
Black trisazo dye. 

Benzip1n, or other, coupled with sulfo dioxy NAPHTHOIC acid and 2-AMINO 8-NAPHTHOL 
6-sulfo “G” then diazotized and coupled with 3-PHENYLENE DIAMIN or other. A sBLaAck direct 
dye. 

Note 557,438. 


557,438—Mar. 31, 1896. J. Scumip, Switzerland. (Basle.) 
Blue dye. 

BENzIDIN, or other, coupled with 2-amino 4-creso. (OH=1) methyl ether, further 
diazotized and coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo, 2 mols., or with 1 mol. of this and 
1 mol. of another comp. A BLUE to BLACK direct and developed dye, that can be diazotized 
on fiber and coupled with phenols, etc. 

S. 353—‘Direct Indigo Blue BN.” and S. 439—Direct Indigo Blue A.” Addition to 
557,427. Schultz gives this pat. under S. 353 but there is no apparent connection. See also 
536,878, 79, and 80, which are classed here by Schulz and 557,435, 36, 37, and 39. 


557,439—Mar. 31, 1896. J. Scumip, Switzerland. (Basle.) 


Polyazo black dye. 

BENzip1n, 2 mols. or other, coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo (or dioxy comp.), 
again diazotized and coupled with 2 mols. 2-aMINo 8-NAPHTHOL 6-sulfo or 1 mol. of this and 
1 mol. of another component. A BLacK direct and developed dye fast to washing, light and can 
be developed on fiber. 

Addition to 557,435. 


557,440—Mar. 31, 1896. J. Scumip, Switzerland. (Basle.) 


Blue-black disazo dye. 
Awniuin, or other, coupled with 1.8-NAPHTHALENE DIAMIN 3.6-disulfo then combined with 
diazo 4-NITRANILIN, or other. A BLACK acid or mordant (Cr) dye, fast to light and milling. 
Near S. 217—‘‘Naphthol Blue Black S.”’ Note 562,200. 


GROUP VI.—AZO 105 


558,344—Apr. 14, 1806. H. A. Berntusen and P. Junius, Germany. (Badische.) 
Blue dye. 


DIANISIDIN coupled with 1-AMINO 5-NAPHTHOL 7-sulfo and 1-NAPHTHOL 4- or 5-sulfo. A 
BLUE direct and developed dye that can be developed on fiber with naphthol, etc. to more violet 
shade. 

S. 345—“Oxamin Maroon” and S. 421—“Oxamin Blue B.’ 


558,612—Apr. 21, 1806. C. RupotepH, Germany. (Oehler.) 
Brown azo dye. (Process also claimed.) 


TOLUYLENE 2.6-DIAMIN 4-sulfo, coupled with 1 mol. each of 2-NAPHTHYLAMIN and 3- 
PHENYLENE DIAMIN, or other, then combined with diazo NAPHTHIONIC acid. Dark brown powd., 
sol. in conc. sulf. (dull V), sol. aq. (YBr), ppt. on diln. (Br); a Brown direct dye. 

Note that first component is a meta diamin. 


558,613—Apr. 21, 1806. Christian Ruponpu, Germany. (Oehler.) 
Oxyquinolin azo dye. (Process also claimed.) 


Dianisip1n coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo, then in alk. soln. with 4-oxy 
QUINOLIN. Green brown powd., of a metallic luster, sol. in aq. (B), in conc. sulf. (GrB); 
violet BLUE direct dye. 

Note that third component has not previously been used in any form. 


558,614—Apr. 21, 18096. Christian RupotpH, Germany. (Oehler.) 
Brown azo dye. (Process also claimed.) 


NAPHTHALENE DIAMIN disulfo, from NAPHTHALENE 3.6-disulfo by dinitration and reduction, 
coupled with 2 mols. BISMARCK BROWN sulfo, (from tetrazotized 2.6-TOLUYLENE DIAMIN 4-sulfo 
coupled with 2 mols. 3-PHENYLENE DIAMIN, or other), and product then combined with 2 mols. 
diazo NAPHTHIONIC acid. Black-brown powd., sol. conc. sulf. (VBr), pptd. on diln., with HCl 
(Br), not changed by NaOH; srowwn direct dye, fast to soap. 


560,448—May 19, 1806. Arthur WEINBERG, Germany. (Cassella.) 
Black azo dye. (Process also claimed.) 


BeEenzIpIN, or other para diamin, coupled in alk. soln. with 2-amMINo 8-NAPHTHOL 3.6-disulfo, 
again diazotized and coupled with 2-am1no 8-NAPHTHOL 6-sulfo “G,’’ further diazotized and 
coupled with 2 mols. 3-PHENYLENE DIAMIN. Or acet. 4-PHENYLENE DIAMIN, coupled in alk. soln. 
with an amino NAPHTHOL sulfo acid, acetyl group removed, tetrazotized and coupled with 
another mol. of an amino NAPHTHOL sulfo acid, then further diazotized and coupled with 2 
mols. of a meta DIAMIN. Black powd., easily sol. hot aq., (BBk), pptd. on diln. (Bk); fast 
BLACK direct dye. 

Note 560,449. 


560,449—May 109, 1896. Arthur WEINBERG, Germany. (Cassella.) 
Black dye. (Process also claimed.) 


DIANISIDIN coupled in alk. soln. with 2-amino 8-NAPHTHOL 6-sulfo “‘G’’ again diazotized 
and coupled with 1 mol. each of 1-AMINO 8-NAPHTHOL 2.4-disulfo and 3-PHENYLENE DIAMIN. Or 
acet. 4-phenylene diamin may be used as first component or the order of coupling may be 
changed. Black powd., easily sol. hot aq. (BBk), insol. alc., ether or benzene, sol. conc. 
sulf. (B), pptd. on diln. (BBk); spiacKk or Gray direct dye. 

Addition to 560,448. 


560,796—May 26, 1896. Meinhard HorrmMann, Germany. 
Blackish-blue azo dye. (Process also claimed.) 


Acet. 1.4-NAPHTHALENE DIAMIN 6- or 7-sulfo, coupled with 1-NAPHTHYLAMIN, or other, 
again diazotized and coupled with naputuionic acid, or other, then saponified. Black powd., 
readily sol. in aq. (B), insol. in alc., sol. in conc. sulf. (B-Bk), pptd. on diln. (B); a dark- 
BLUE direct dye. 

S. 274—“Diaminogen B.” Addition to 533,463. 


561,615—June 9, 1806. Friedrich RunKEL, Germany. (Bayer.) 
Red azo dye. (Process also claimed.) 

Ethyl 4-amino sENzorc acid coupled in acetic acid soln. with 1.8-dioxy NAPHTHALENE 4- 
sulfo. Brown powd. with green luster, easily sol. hot aq. and alc. (R), sol. in conc. sulf. 
(B-Bk), pptd. on diln. (R); violet-rEp acid dye, fast to alk. 


106 DIGEST OF PATENTS 


561,694—June 9, 1896. 
August Branx, Adolf Israri, and Martin Hersperc, Germany. (Bayer.) 
Black azo dye and process of making same. 

DianisipIn coupled in alk. soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo, soln. made acid 
with acetic and 3-PHENYLENE DIAMIN, then diazo acetyl 4-PHENYLENE DIAMIN added and soln. 
made alk. Other components are claimed, also a different order of coupling. Black powd. sol. 
in aq. (V-B), almost insol. in alc., sol. conc. sulf. (B-Bk), pptd. on diln. (B); sLacx direct dye. 
fast to alk. and acid. 

Note 561,709. 


561,709—June 9, 1896. 
Martin Hersperc, August BLranx, and Adolf Israrr, Germany. (Bayer.) 
Black azo dye. (Process also claimed.) 

BENzIDIN coupled in acid soln. with 1 mol. each of 1-AMINO 8-NAPHTHOL 3.6-disulfo 
and 3-PHENYLENE DIAMIN then combined in alk. soln. with diazo acetyl 4-PHENYLENE DIAMIN. 
Other components and a different order of coupling are claimed. Black powds., sol. in aq. (Bk), 
almost insol. in alc., etc., sol. conc. sulf. (B-Bk), pptd. on diln. (Bk); Brack direct dyes, fast 
to alk. and acid. 

Addition to 561,694. 


562,200—June 16, 1806. Jakob ScuMmip and Karl Jepiicxa, Switzerland. (Basle.) 
Dark-green dye. (Process also claimed.) 

1.8-NAPHTHALINE DIAMIN 3.6-disulfo combined in neutral or acetic acid soln. with 1 mol. 
each of diazo ANILIN and diazo 4-NITRANILIN, then product condensed in acetic acid soln. by 
boiling until color shade is satisfactory. (NH, is evolved). Other components claimed. Dark 
powd. with bronze luster, easily sol. aq. (GB-G), sol. conc. sulf. (BG), slightly sol. in alc., 
insol. in ether and benzene; GREEN to BLACK acid and acid mordant (Cr) dyes, fast to washing 
and light. 

Note 557,440. 


563,383—July 7, 18096. Friedrich Krecxe and Ignaz RosENBEeRG, Germany. (Kalle.) 
Azo dye. (Process also claimed.) 

ANILIN or other amino or amino-azo bodies, coupled with 1-AMINO 8-NAPHTHOL 4.6-disulfo, 
“K” acid. Cryst. bronzy powd., easily sol. in aq., almost insol. in alc.; red to dark BLUE 


acid dyes. 
S. 43—“Tolan Red B.” Note 563,384, 563,385 and -6. 


563,384—July 7, 1806. Friedrich Krecxe and Ignaz RosenBerc, Germany. (Kalle.) 
Disazo dye. (Process also claimed.) 

SuLFANILIC acid or other, coupled with 1-amMino 8-NAPHTHOL 3.6-disulfo, ‘‘K” acid, then 
with diazo 4-NITRANILIN, or other. Cryst. powd. of reddish-bronze color, easily sol. in aq., - 
diff. sol. in ale.; BLUE to GREEN acid and direct dyes. 

S. 31s—“Blue black N.” Schulz credits patent to Elbel and Rosenberg, 1896. Note 
563,385. 563,386, and 613,638. 


563,385—July 7, 1896. Friedrich Krecksé and Ignaz Rosenserc, Germany. (Kalle.) 
Blue tetrazo dye. (Process also claimed.) 

Benzip1x, or other diamin, or their sulfo or carbo acids, coupled with a mols. 1-AMINO 
8-NAPHTHOL 4.6-disulfo, ““K’ acid. Cryst. powd. of yellow-bronze color, sol. in aq., almost 
insol. in alc.; violet BLUE direct dye which can be diazotized on fiber. 

S. 338.—Naphthylamin Blue 2B.” Note 563,334 and 563,335. 


563,386—July 7, 1896. Friedrich Krecxe and Ignaz RoseNnBERG, Germany. (Kalle.) 
Greenish-blue tetrazo dye. 


DIANISIDIN, or other diamin coupled with 1-AMINO 8-NAPHTHOL 4.6-disulfo “K” and 1- 
AMINO 8-NAPHTHOL 3.6-disulfo “H,’ or other. Bronzy cryst. powd., easily sol. aq. almost 


insol. alc.; BLUE tO VIOLET to BROWN direct dyes, 
S. 335—‘‘Naphthylamin Black RE” and §S. 338—‘‘Naphthylamin Blue 2B.” Note 563,383, 


563,384 and 563,385. 


GROUP VI.—AZO 107 


567,413—Sept. 8, 1806. Christopher Ris, Switzerland. (Geigy.) 
Brown diazo dye and method of making same. 


BENZIDIN, or other, coupled with saticy1ic acid or homolog and dialkyl 2-AMINO 8-NAPHTHOL 
6-sulfo. Dark-brown powd., sol. in aq. (Br), in conc. sulf. (VB), pptd. by acids (R), decomp. 
on reduction; fast BROwN direct dyes. 

S. 334—‘Diphenyl Blue Black,” also S. 347, 348 and 398 Addition to 566,166. 


567,615—Sept. 15, 1806. Friedrich RunxrEL, Germany. (Bayer.) 
Blue azo dye. (Process also claimed.) 


as-Dimethyl 4-PHENYLENE DIAMIN coupled with 1.8 dioxy NAPHTHALENE 4-sulfo “S.”? Dark 
bronzy powd., diff. sol. in cold aq., sol. alc. and hot aq. (B), with NH, (R), sol. conc. H,SO, 
(V), on diln. (R-B); siue acid dye. 

S. 63—‘“‘Azo Acid Blue B.” 


568,549—Sept. 29, 1896 Christian RupoLpH and Emil Vocrs, Germany. (Oehler.) 
Yellow dye. (Process also claimed.) 

2.6-TOLUYLENE DIAMIN 4-sulfo coupled with nitro 3-PHENYLENE DIAMIN. Light-brown powd., 
sol. in aq. (Y), pptd by acid; yELLow direct dye. 

S. 286—‘“‘Toluylene Yellow.” 


569,392—Oct. 13, 1896. Fritz Storcx, Germany. (Hochst.) 
Process of producing azo colors on fiber. Producing fast insol. azo colors on fiber 
by use of cupric chloride. 

Goods padded with 2-NapuHtuor and Turkey Red oil, dried and printed with soln. of tetrazo 
DIANISIDIN containing cupric chloride, gum, etc. Other azo dyes may be similarly treated 
and advantages of process as compared with 2-oxy naphthoic developer, other copper salts, 
etc., are given. Though in the form of an application to the fiber, the dye is new. BLuE 
developed dye. 

S. 408—“Dianisidin Blue.” 


569,395—Oct. 13, 1896. Eduard Uuiricu and Moritz von Gatiois, Germany. (Ho6chst.) 
Process of dyeing phenetidin red. 

2-Nitro 4-PHENETIDIN coupled with 2-NAPHTHOL on the fiber, as dye or printing comp. 
Though presented in form of application to the fiber, this dye is new Violet-rED developed 
dye suitable for printing. 


571,933—Nov. 24, 1896. Christopher Ris, Switzerland. (Geigy.) 
Black triazo dye. (Process also claimed.) 

Benzipin, homologs or derivs., coupled with alkylated 2-amMINo 8-NAPHTHOL 6-sulfo and 
nonalkylated 2-AMINO 8-NAPHTHOL 6-sulfo, again diazotized and coupled with RESORCIN, or 
other. Black powd., sol. in H,SO, (GrB), decomp. by reducing agents; Gray to deep BLACK 
direct dyes. 


572,723—Dec. 8, 1806. Christian RupotpH, Germany. (Oehler.) 
Trisazo dye. (Product also claimed.) 

Benzip1n, or other, coupled with 3-amino PHENOL 6-sulfo and with 3-PHENYLENE DIAMIN, 
or resorcin, then diazo NapHTHIONIC acid added. A black powd., sol. in aq. (Br-BrR), sol. 
in H,SO, (V-B); brown-rEp direct dye. 

S. 480—“Congo Brown R.” Schulz credits dye to Strazburger, 1888. 


575,904—Jan. 26, 1807. Christopher Ris, Switzerland. (Geigy.) 
Black azo dye. (Process also claimed.) 

4.4'-Diamino pIToLyL amin, tetrazotized and coupled with 2-AMINO 8-NAPHTHOL 6-sulfo or 
alkylated derivs. and 3-PHENYLENE DIAMIN. Or, after coupling with the first component it is 
further diazotized and coupled with a second mol. of same, then with 3-PHENYLENE DIAMIN, or 
other. Black powd., sol. in aq. (B-Bk), in H,SO, (B); blue-siacx direct dye. 

S. 2z95—‘‘Diphenyl Fast Black.” 


576,511—Feb. 2, 1897. Georg StEINIKE and Friedrich Scumipt, Germany. (Ho6chst.) 
Blue trisazo dye. (Process also claimed.) 

1.8-Dioxy NAPHTHALENE 4-sulfo “S,” coupled with diazo NAPHTHIONIC acid, or other diazo 
comp., then with tetrazotized BENZIDIN, or other tetrazo comp., finally combined with 1-AMINO 


8 


108 DIGEST OF PATENTS 


8-NAPHTHOL 3.6-disulfo “‘R,” or other phenol, naphthol, or deriv. Gray-black powd., sol. in 
aq. (V-B), H,SO, (B), pptd. on diln. (V); vroter to deep siack direct dyes, fast to light 
and soap. 

Note 444,679, among Intermediates. 


578,432—Mar. 9, 1897. Moritz Uxricu and Johann Bammann, Germany. (Bayer.) 
Dark-blue azo dye. (Process also claimed.) 

BENZIDIN, or homolog, coupled with 2-AMINo 8-NAPHTHOL 3.6-disulfo, then with 1-AMINO 
8-NAPHTHOL 4-sulfo. Dark powd., sol. in aq. (B-Bk), almost insol. alc., sol. NaOH (V-B), 
H,SO, (G-B), on diln. (V-B), then pptd. (V), pptd. by acetic acid; srux direct and developed 
dyes, fast to alkali and acid that can be diazotized on fiber and coupled to form darker and 
faster shades. 

S. 236—‘‘Benzocyanin R,” S$. 390—‘‘Benzocyanin B,’’ and S. 425—‘“‘Benzocyanin 3B.” 
Addition to 539,608. 


578,580—Mar. 9, 1897. Ferdinand Prrrersen, Switzerland. (Petersen.) 
Substantive cottom dye. (Process also claimed.) 

BENZIDIN disulfo, or homolog, coupled with 2 mols. 2-AMINo 8-NAPHTHOL 6-sulfo ‘‘G,” 
tetrazotized and coupled with 2 mols. 3-PHENYLENE DIAMIN, or other aromatic amino comp. 
A black powd., readily sol. in aq. (R-Br), insol. alc., sol. in H,SO, (B-G), pptd. with HCI 
(RBr), with caustic soda (Br); rep, violet-sLuE to blue-BsLAcK direct and developed dyes, fast 


to light and washing. 
S. 491—“‘Dianil Black P.R.” 


579,773—Mar. 30, 1897. Christian Rupotpu, Germany. (Oehler.) 
Red-blue diazo dye. (Process also claimed.) 

BENzIpDIN, or homolog, coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo “H,” then with 2.3- 
dioxy NAPHTHALENE. Dark brown powd., sol. in aq., (V), in H,SO, (B); violet-sLug direct 
dye. 


582,958—May 18, 1897. Friedrich Scumipt and Otto Ernst, Germany. (Hdchst.) 
Trisazo dye. (Process also claimed.) 

1.8-Dioxy NAPHTHALENE 4-sulfo “S’’ coupled with diazo NAPHTHIONIC acid, then with tetrazo 
BENZIDIN, and finally with 3-TOLUYLENE DIAMIN. Grayish-brown powd., sol. in aq. (B-V), with 
NaOH (dull RV), sol. H,SO, (B); blue-Bnacx direct and developed dyes, that can be diazotized 
on fiber. 

Near S. 479—‘“Dianil Black B.” Note 582,959. 


582,959—May 18, 1897. Friedrich Scumipt and Otto Ernst, Germany. (Hoéchst.) 
Trisazo dye. (Process also claimed.) 

1.8-Dioxy NAPHTHALENE 4-sulfo “S,” coupled with diazo NapuTHionic acid, then with 
tetrazo BENZIDIN, and finally with 1-NAPHTHYLAMIN. A violet-brown powd., sol. in aq. (B-V), 
with NaOH (dull-RV), sol. H,SO, (B); blue-sLacx direct and developed dyes. 

Near S: 479—‘‘Dianil Black R.” Addition to 582,958. 


583,439—May 25, 1897. W. Herzserc and O. Hensmann, Germany. (Berlin.) 
Black azo dye. 

Picramic acid, coupled with 1-NAPHTHYLAMIN 6-sulfo, then diazotized again and coupled 
with 2-NAPHTHOL. VIOLET to BLACK acid and developed (CrO,) dye, which after chroming is 
fast to fulling, alk., acids and light. 


583,634—June 1, 1897. Jakob Scum and Karl Jxepuicxa, Switzerland. (Basle.) 
Black trisazo dye. (Process also claimed.) 

4-Amino BENZALDEHYDE, or other, coupled with 1-AMINOo 8-NAPHTHOL 3.6-disulfo “H” or 
other, then with tetrazotized BENZzIDIN or any diamino base, finally with 3-roLuYLENE DIAMIN, or 
other aromatic meta diamin. A dark powd., insol. in alc., ether and benzene, sol. in aq. 
(VBk-BBk), sol. H,SO, (B); sracx direct and developed dyes which can be condensed on 
fiber with aromatic hydrazins. : 

Addition to 582,958. 


GROUP VI.—AZO 109 


583,635—June 1, 1897. Jakob Scumip and Karl JepLicKa, Switzerland. (Basle.) 
Blue trisazo dye. (Process also claimed.) 


3-Amino BENzorc acid, coupled in alk. soln. with 1-amMINo 8-NAPHTHOL 3.6-disulfo, more 
carbonate added and soln. combined with one equivalent of tetrazo DIANISIDIN, then coupled 
with I-AMINO 8-NAPHTHOL 3.6-disulfo. Other similar components claimed. A powd. of bronze 
luster, insol. in alc., ether and benzene, sol. in aq. (B-G), sol. H,SO, (B), pptd. on diln.; a 
BLUE direct dye. 


584,981—June 22, 1897. Melchior BénicEr, Switzerland. (Basle.) 
Blue dye. (Process also claimed.) 

DiansiDIN coupled with 1-NAPHTHOL 3.6.8-trisulfo, then with 2-naputHoL. A bronze powder, 
sol. in aq. (B), not changed by Na,CO,, with NaOH turns (R-V) sol. in methyl but very 
weakly in ethyl alc. (V), sol. conc. H,SO, (G-B), in boiling salt (B); sius direct dye. 

S. 322—‘Trisulfon Violet B,” S. 388—‘Trisulfon Blue R,” and S. 409—‘‘Trisulfon 
Blue B.” 


585,104—June 22, 1897. Karl Jepiicka, Switzerland. (Basle.) 
Green triazo dye. (Process also claimed.) 

3-Amino BENZorIC, or deriv., coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo “HH,” then com- 
bined with tetrazo rotip1n, homolog or derivs, and finally with pHENoL, homolog or deriy. A 
bronzy powd., insol. in alc., ether and benzene, sol. in aq. (G), sol. H,SO, (dull BV); cream 
direct or acid mordant (Cr) dye, fast to light and alks. 

Addition to 582,958. 


586,865—July 20, 1897. Emil von Porturrm, Austria-Hungary. 
Process of dyeing black. 

Amino CHRYSOIDIN (triamino azo benzene) diazotized or tetrazotized and coupled on fiber 
previously prepared witih 2-NaAPHTHOL. Brack developed dye, fast to light. Although patent 
takes the form of an application to the fiber, dye is new. 

S. 259—‘“‘Ice Black.” 


588,180—Aug. 17, 1897. Ignaz RosEnBERG, Germany. (Kalle.) 
Bluish-searlet dye. (Process also claimed.) 

Dehydro thio ToLuip1n sulfo or other aromatic amin, coupled with 1.3-NAPHTHALENE DIAMIN 
6-sulfo. Brown-red bronzy powd., easily sol. aq. insol. alc., sol. H,SO, (V), alk. reduction with 
Zn (Y), with air (B-R); vari-colored direct dyes, fast to washing, light, alks. and acids. 

Note 587,757. 


588,181—Aug. 17, 1897. Ignaz RosEnsBEerG, Germany. (Kalle.) 
Reddish-violet dye. (Process also claimed.) 

DIANISIDIN, or other diamin, coupled with 2 mols. NAPHTHALENE 1.3-DIAMIN 6-sulfo. A 
black bronzy powd., easily sol. hot aq., insol. in alc., sol. in H,SO, (B), on alk. reduction with 
Zn, a colorless soln.,-turning to (Br) under influence of air; dyeing unmordanted cotton (RV), 
which on treatment is changed to (BrV); vari-colored direct and developed dyes, fast to light, 
washing, alkali and acids, which can be diazotized on fiber and coupled with naphthols, etc. 

Note 588,182 and 588,183. 


588,182—Aug. 17, 1897. Ignaz Rosenserc, Germany. (Kalle.) 
Mixed substantive dye. (Process also claimed.) 

BENZIDIN or similar diamin coupled with 1.3-NAPHTHALENE DIAMIN 6-sulfo and NAPHTHIONIC 
acid or other amin. A black bronze powd., easily sol. hot aq., insol. in alc., sol. H,SO, (B), on 
alk. reduction with Zn (Y), turning (Br) with air; vari-coLoRED direct and developed dyes, 
which can be diazotized on fiber. 

Addition to 588,181. 


588,183—Aug. 17, 1897, Ignaz Rostnserc, Germany. (Kalle.) 
Brown substantive dye. (Process also claimed.) 

Benzip1in, or homolog, coupled with saticytic acid, then with 1.3-NAPHTHALENE DIAMIN 
6-sulfo, again diazotized and coupled with 3-ToLUYLENE DIAMIN, or other amin, phenol, sulfo or 
carbo acid. Dark-brown powds. sol. in aq., insol. alc., sol. H,SO, (RV), alk. reduction with 
Zn (colorless), with air (Br); fast Brown to BLACK direct dyes. 

Addition to 588,181. 


LTO DIGEST OF PATENTS 


588,203—Aug. 17, 1897. Arthur WEINBERG, Germany. (Cassella.) 


Process of developing azo dyes. Using diazo comps. for developing substantive azo 
colors, having free primary amino groups. 


Fibers dyed with pDIAMIN BLACK, etc., passed through acid, alk., or neut. bath of diazo 
4-NITRANILIN, or Other diazo comp. ‘Table of components and resultant colors is given; VARI- 
colored direct and developed dyes, fast to milling, acids, rubbing, etc. 

Near S. 401—‘‘Diamin Blue 3R,” also 402 and 403, ‘‘Diamin Black BO.” 


590,088—Sept. 14, 1897. Carl Biitow, Germany. (Badische.) 
Black disazo dye. 


I-AMINO 8-NAPHTHOL 4-sulfo, coupled with diazo sULFANILIC acid, then with diazo 1-NAPH- 
"HYLAMIN, or other, in acid or alk. soln. for either coupling, preferably acid first and alk. 
second. A BLACK direct dye. 

S. 220—‘‘Palatin Black A.’? Note 593,790 and the above are apparently identical. 


591,616—Oct. 12, 1807. Melchior BOnicER, Switzerland. (Sandoz.) 
Trisazo dye. (Process also claimed.) 


BENZIDIN, or other para diamin, coupled with 4-xy1iip1n, diazotized and again coupled. with 
2 mols. I-AMINO 8-NAPHTHOL 3.6-disulfo ‘‘H.”? Biur to BLACK Or GREEN direct dyes, which may 
be diazotized on fiber. 

S. 438—‘‘Melanogen Blue B H.” 


593,347—Nov. 9, 18097. Fritz BrEnpER, Germany. (Leonhardt.) 
Violet disazo dye. 


SULFANILIC acid, or substituted amin usually not capable of yielding direct azo dyes, coupled 
with ANILIN, or similar amino compound or deriv., recoupled in alk. soln. with ethyl 2-amino 
5-NAPHTHOL 7-sulfo. Rep to vioLET direct dyes. 


593,790—Nov. 16, 1897. Moritz Utricu and Johann Bammann, Germany. (Bayer.) 
Blue-black disazo dye. (Process also claimed.) 


SULFANILIC acid coupled in weak mineral acid soln. with 1-AMINO 8-NAPHTHOL 4-sulfo, then 
combined with diazo 1-NAPHTHYLAMIN. BLack acid dye, fast to alk., acid and light. 
S. 220—‘‘Palatin Black A.”? Note 590,088 is apparently a duplicate of the above. 


594,123—Nov. 23, 1897. Christian H. Rupoipu and Julius Herpasny, Germany. (Oehler.) 
Blue-red tetrazo dye. (Process also claimed.) 


2.2’-Dichlor BENZIDIN, coupled with 2 mols. of 2-NAPHTHYLAMIN 3.6-disulfo (Amino R salt). 
S. 358—“‘Brill. Dianol Red R.” Schulz credits this dye to Pfeiffer, 1896. 


594,996—Dec. 7, 1897. Myrtil Kaun and Friedrich RunxeL, Germany. (Bayer.) 
Blaek azo dye. (Process also claimed.) 


4.4/-Diamino DIPHENYLAMIN 2-sulfo, coupled with 1 mol. each of 1-NAPHTHYLAMIN 6- or 7- 
sulfo, and 2-AMINO 8-NAPHTHOL 6-sulfo “G,” then tetrazotized and coupled with 2 mols. 3-PHE- 
NYLENE DIAMIN, or other meta diamin. 

Note 595,021. 


595,021—Dec. 7, 1897. Myrtil Kaun and Friedrich Runxet, Germany. (Bayer.) 
Black azo dye. (Process also claimed.) 


4.4/-DIPHENYLAMIN 2-sulfo, coupled with 2 mols. 2-amiIno 8-NAPHTHOL 6-sulfo “G,” then 
tetrazotized and coupled with 2 mols. 3-PHENYLENE DIAMIN. A BLACK direct dye, fast to acids, 
alks. and especially light. 

Addition to 594,996. 


599,532—Feb. 22, 1808. Christopher Ris, Switzerland. (Geigy.) 
Black trisazo dye. (Process also claimed.) 


4-Amino ACETANILID, or 4-nitranilin, coupled with 2-AMINO 8-NAPHTHOL 6-sulfo ‘‘G,” reduced 
or saponified, then tetrazotized and coupled with 1 mol. each of 3-PHENYLENE DIAMIN, or other, 
and 2-amino 8-NAPHTHOL 6-sulfo in acid then alk. soln. A sack direct dye, fast to soap. 


GROUP VI.—AZO Tit 


601,0383—Mar. 22, 1808. Melchoir BénicER, Switzerland. (Geigy.) 
Blue-blaeck mixed trisazo dye. 

2-Amino 8-NAPHTHOL 3.6-disulfo ‘“2R,” coupled with 1-NAPHTHYLAMIN, then with tetrazo 
BENZIDIN, or Other, and 2-AMINO 8-NAPHTHOL 6-sulfo “G,” or other. Buus to violet-Buack direct 


and developed dyes, which can be coupled on fiber to form shades fast to washing. 
S. 442—‘“Direct Black V,” and 443—‘“Direct Indon Blue.” 


601,859—Apr. 5, 1898. Christian RupotepH, Germany. (Oehler.) 
Blue azo dye. (Process also claimed.) 


To.ip1n, or benzidin, coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo then with 2.6-dioxy NAPH- 
THALENE, both in alk. soln. A BLueE direct dye. 


602,637—Apr. 19, 1808. Ernst Konic, Germany. (Hoéochst.) 
Basic red disazo dye. 

Trimethyl ammonium 3-PHENYLENE DIAMIN salt, coupled with 3-ro_uipiIn, again diazotized, 
coupled with 2-NaPHTHOL. <A RED basic and basic mordant dye. 

Near S. 435—‘“‘Janus Brown B R.” Note 602,638, 39 and 40, 610,345, 623,697 and 626,913. 


602,638—Apr. 19, 1808. Ernst K6nic, Germany. (Héchst.) 
Basie yellow disazo dye. 
Trimethyl ammonium 3-PHENYLENE DIAMIN salt, coupled with 3-roLuipiINn, then with phenyl 


methyl PYRAZOLONE. YELLOW basic and basic mordant dyes. 
S. 435—‘“Janus Brown B.” Note 602,637, 602,639 and 40, 610,345, 623,697 and 626,913. 


602,639—Apr. 19, 1898. Ernst Konic, Germany. (Héchst.) 
Coppery-brown dye. 
Trimethyl ammonium 3-PHENYLENE DIAMIN, coupled with 3-ToLuIpIN, then with CHRYSOIDIN. 


A BRown basic mordant dye. 
S. 435—‘“Janus Brown B.”’ Addition to 602,637. 


602,540—Apr. 19, 1898. Myrtil Kaun, Germany. (Elberfeld.) 
Violet dye. (Process also claimed.) 


DIANISIDIN, coupled with 1 mol. each of 2-NAPHTHOL 3.6-disulfo “‘R’’ and 4-xyLipIn. A 
VIOLET direct dye. 


602,640—Apr. 19, 1898. Ernst Konic, Germany. (Hochst.) 
Red violet basic disazo dye. 

Zinc chloride salt of trimethyl ammonium 3-PHENYLENE DIAMIN azO CRESIDIN, ethyl ether, 
coupled with 2-NapHTHOL. Red vioLet basic and basic mordant dye. 

S. 435—“Janus Brown B.” 


602,641—Apr. 19, 1898. Ernst Konic, Germany. (Hochst.) 
Brown disazo dye. (Process also claimed.) 


4’-Amino PHENYL trimethyl ammonium chloride, coupled with 1-NAPHTHYLAMIN, again 
diazotized and coupled with cuHrysorpIN. Other components claimed. 


602,855—Apr. 26, 1808. Karl Krexeter and August BLanK, Germany. (Elberfeld.) 


Blue-black trisazo dye. (Process also claimed.) 

Toipin, or other, coupled with 2-AMINO 8-NAPHTHOL 6-sulfo “G’”’ then diazotized and coupled 
with 2 mols. 1.8-dioxy NAPHTHALENE 4-sulfo “S.” BuueE to blackish-BLuE direct and developed 
(CrO, or Cu) dyes fast to acids, alks., darker when after chromed or coppered. 

Note 602,856, 57, 58, and also 603,008, 09 and go. 


602,856—Apr. 26, 1898. Karl KrexeLer and Adolf Isrart, Germany. (Elberfeld.) 


Black trisazo dye. (Process also claimed.) 

Toxin, or other, coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo,, then diazotized and coupled 
with 2 mols. 1.8-dioxy NAPHTHALENE 4sulfo. Buiug and siacx direct and developed (CrO, or 
Cu) dyes, very fast after treatment with metallic salts. 

Near S. 452—‘‘Benzo Indigo Blue.” Addition to 602,855. 


II2 DIGEST OF PATENTS 


602,857—Apr. 26, 1808. 
Karl Krexeer, Adolf Isrart, and August BLanx, Germany. (Elberfeld.) 
Black trisazo dye. (Process also claimed.) 
ToLIpDIN, or other, coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo ‘‘Cleve’s,” then diazotized 
and coupled with 1 mol. each of 1.8-dioxy NAPHTHALENE 4-sulfo “S” and 3-TOLUYLENE DIAMIN, OF 
homologs. Buacxk direct and developed dyes, which when treated with metallic salts are fast 


to washing. 
Addition to 602,855. 


602,858—Apr. 26, 1808. Karl KrexeLer and Eduard Martz, Germany. (Elberfeld.) 
Brown trisazo dye. (Process also claimed.) 

BENZIDIN, or other, coupled with 1 mol. each of saticyLic acid, or other ortho oxy carbo 
acid of benzene series, and I-NAPHTHYYLAMIN 6-sulfo “‘Cleve’s,” again diazotized and coupled 
with another mol. saricyiic acid, etc. Brown acid or developed (CrO,, Cu) dye, fast to milling 
and washing when chromed. 

Addition to 602,855. 


603,008—Apr. 26, 1808. Myrtil Kaun, Germany. (Elberfeld.) 
Violet azo dye. (Process also claimed.) 

BENZIDIN, or other, coupled with 2 mols. 1-AMINO 8-NAPHTHOL 4-sulfo “‘S.”? Black vroLEeT 
direct and developed (coupled) dye, fast to acids and washing when coupled on fiber with diazo 
4-nitranilin. 

S. 425—‘Benzocyanin 3 B.’”’ Note 602,855 et. seq., 603,009 and 90, 603,645, 46, 47, 48 
and 603,103. 


603,009—Apr. 26, 1808. Myrtil Kaun and Friedrich RunxreL, Germany. (Elberfeld.) 
Bluish-red dye. (Process also claimed.) 

4.4’-Diamino DIPHENYLAMIN 2-sulfo, coupled with 2 mols. 3-PHENYLENE DIAMIN. Rep and 
BROWN direct and developed dyes, fast to washing when coupled on fiber with diazo 4-ni- 
tranilin. 

Addition to 603,008. 


603,090—Apr. 26, 1898. Karl KreKELER and Eduard Martz, Germany. (Elberfeld.) 
Brown trisazo dye. (Process also claimed.) 

BENzIDIN, or other, coupled with 1 mol. each of sanicy1ic acid and I-NAPHTHYLAMIN 6-sulfo 
““Cleve’s,” then diazotized again and coupled with 3-ToLUYLENE DIAMIN 6-sulfo, other meta 
diamin of benzene series, or sulfo acid thereof. 

Addition to 603,008. 


603,093—Apr. 26, 1898. Georg STEINIKE and Friedrich ScuMmipt, Germany. (Hdéchst.) 
Black disazo wool-dye. (Process also claimed.) 

1.8-Dioxy NAPHTHALENE 4-sulfo “S,’? coupled with diazo NAPHTHIONIC acid, then with diazo 
I-NAPHTHYLAMIN, or other amin, both in alk. soln. A blue BLacx acid and developed (CrO,) dye. 


603,645—May 10, 1898. Karl KrEKELER and Eduard Martz, Germany. (Elberfeld.) 
Green trisazo dye. (Process also claimed.) : 
Benzip1Nn, or other, coupled with 1 mol. each of saticyLic acid and 1-NAPHTHYLAMIN 6-sulfo, 
then diazotized and coupled with 1-AMINO 8-NAPHTHOL 2.4-disulfo, or other all in alk. soln. 
Addition to 603,008. 


603,646—May 10, 1898. 
Karl KrexeLer, Eduard Martz, and Adolf Isrart, Germany. (Elberfeld.) 
Gray trisazo dye. (Process also claimed.) 

Benzipin, or homologs, coupled with 1 mol. each of SALICYLIC acid, or other ortho oxy 
carbo acid, and 1-NAPHTHYLAMIN 6-sulfo, then diazotized and coupled with I-NAPHTHOL 4- or 
s-sulfo. A green-cray direct dye. 

Addition to 603,008. 


GROUP VI.—AZO rt 


603,647—May 10, 1808. 
Karl Krexeier, Eduard Martz, and Adolf Israrz, Germany. (Elberfeld.) 
Green trisazo dye. (Process also claimed.) 
Benzip1n, coupled with 1 mol. each of saLicynic acid and 1-NAPHTHYLAMIN 6-sulfo, then 
diazotized and coupled with 1.8-dioxy NAPHTHALENE 4-sulfo, or other. 
Addition to 603,008. 


603,648—May to, 1808. 
Karl KrexELerR, Eduard Martz, and Adolf Israri, Germany. (Elberfeld.) 
Brown trisazo dye. (Process also claimed.) 

Benzipin, coupled with 1 mol. each of sanicyLtic acid and 1-NAPHTHYLAMIN 6-sulfo, then 
diazotized and coupled with a second mol. of the latter. Brown direct, acid and developed 
(CrO,) dye, faster to milling when chromed. 

Addition to 603,008. 


605,103—June 7, 1808. Myrtil Kaun and Karl Hemernreicu, Germany. (Elberfeld.) 
Black disazo dye and process of making same. 

4-Amino DIPHENYLAMIN 2-sulfo, coupled with 1-NAPHTHYLAMIN, then diazotized and coupled 
with 1-NAPHTHOL 5- or 4-sulfo. A BLack direct dye, fast to milling and light. 

Addition to 603,008. 


606,181—June 28, 1808. Johann BamMMANN, Germany. (Elberfeld.) 
Blue tetrazo dye and process of making same. 
BENZIDIN, or other, coupled with 2 mols. 1-AMINO 8-NAPHTHOL 4.6-disulfo “K.”’ in alk. soln. 


A sBLuE direct dye, fast to acids and alks. 
S. 338—‘“‘Naphthamin Blue 2B.’”’ Note 606,264. Schulz credits this dye to Krecke and 


Rosenberg, 1896. (Pat. 563,385, etc.) 


606,264—June 28, 1808. Johann BAMMANN, Germany. (Elberfeld.) 

Dark-blue tetrazo dye and process of making same. (Pnoduct only claimed.) 
Brnzip1n, or homolog, coupled with 1 mol. each of 1-AMINO 8-NAPHTHOL 4.6-disulfo “K” and 

2-AMINO 8-NAPHTHOL 6-sulfo “G.”? A blackish BLUE direct dye, that can be diazotized on fiber. 
Addition to 606,181. 


606,436—June 28, 1898. Fritz Benprr, Germany. (Leonhardt.) 


Blue dye. 

Totip1n, or other, coupled with 2 mols. 1-AMINO 8-NAPHTHOL 3.5-disulfo “B’’ (from amino 
8-naphthol 3-sulfo, by sulfonation) in alk. soln., or 1 mol. of this and a second mol. of 2-NAPH- 
"HOL or homolog. 2-NAPHTHYLAMIN can be also used as middle component. A sue direct dye. 

S. 389—‘“Eboli Blue B,” and S. 466—‘‘Eboli Green CR.” Note 606,438 and 606,439. 


606,438—June 28, 1808. Fritz Benprer, Germany. (Leonhardt.) 


Blue-black dye. 

ANILIN, or other aromatic amin, coupled with 1-AMINO 8-NAPHTHOL 3.5-disulfo “‘B,” then 
product combined with diazo 4-NITRANILIN, both in alk. soln. A BLACK acid dye. 

S. 216—‘‘Domingo Blue Black B.” Also S. ‘389 and 466. 


606,439—June 28, 1808. Fritz BenpeR, Germany. (Leonhardt.) 


Green disazo dye. 
SuLFANILIC acid, or other, coupled in alk. soln. with 1-AMINO 8-NAPHTHOL 3.5-disulfo “B,” 


and diazo BENZIDIN azo sALIcyLic acid, or homolog. Other methods outlined, coupling com- 


ponents in different order. 
S. 889—“Eboli Blue B.” Note 606,436 and -7. 


608,024—July 26, 1808. Melchior Bonicer, Switzerland. (Sandoz.) 


Brown azo dye. (Process also claimed.) 
2-AMINO 8:NAPHTHOL 3.6-disulfo, coupled with 3-TOLUYENE DIAMIN, then combined with diazo 
NAPHTHIONIC acid, or other, again coupled with diazo BENZIDIN azO SALICYLIC acid. Brown direct 


114 DIGEST OF PATENTS 


or developed (CrO, Cu) dye, fast to light and soap, deepened in shade by after chroming or 
coppering. 
S. 449—“Trisulfon Brown B.”? Also S. 454 and 457. 


608,999—Aug. 16, 1808. Johann BAMMANN and Moritz Uuricu, Germany. (Bayer.) 
Blue-black azo dye. (Process also claimed.) 


BENZIDIN, coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo, then with 1-NAPHTHYLAMIN. VIOLET 
to BLACK direct and developed (coupled) dye, which can be diazotized and coupled on fiber. 


S. 382—‘‘Azo Mauve B,” and S. 383—‘‘Naphthazarin B.” Addition to 463,415. 


610,345—Sept. 6, 1808. Bernhard Drtcxe, Germany. (Hochst.) 
Red acid dye and process of making it. 


4-Amino BENZYL diethylamin, or alkyl deriv., coupled with 3-ro.u1pin, or other, then diazo- 
tized again and coupled with 2-NaPpHTHOL, phenol, pyrazolone, amino or oxy-azo comp. 


S. 435—‘‘Janus Brown D.” Note 602,637, et seq. 


610,849—Sept. 6, 1808. Otto Ernst, Germany. (Hochst.) 
Violet azo dye and process of making it. 

I-AMINO 8-NAPHTHOL 4-sulfo, coupled with 1-NAPHTHYLAMIN. VIOLET or BROWN acid or 
developed (CrO,) dyes, when after chromed are fast to milling and light. Graphic formulas in 
patent show beta naphthylamin, while text gives alfa comp. 


610,367—Sept. 6, 1808. Alfred Puitips, Germany. (Hochst.) 
Basic disazo dye. (Process also claimed.) 

Amino azo BENZENE, coupled with 2-NAPHTHOL 7-trimethyl ammonium chloride. A RED 
basic dye. 


611,111—Sept. 20, 1898. . Emil Eusagsser, Germany. (Dahl.) 
Brown dye and process of making it. 

BENZIDIN, Or homolog, coupled with 1 mol. each of bisulfite comp. of I-NITROSO 2-NAPHTHOL 
and 2-AMINO 8-NAPHTHOL 6-sulfo. A sBRown direct dye. 

S. 331—‘‘Alkali Dark Brown.” 


611,597—Oct. 4, 1898. Johann BaMMANN, Germany. (Elberfeld.) 
Green-blue tetrazo dye. (Process also claimed.) 

DIANISIDIN, or other, coupled with 1 mol. each of 1-AM1No 8-NAPHTHOL 4.6-disulfo ‘‘K,” 
and 1-AMINO 8-NAPHTHOL 3.6-disulfo “H,’? or other naphthol or naphthylamin sulfo acid. Violet 
BLUE direct or developed (coupled) dye, fast to acids, alks., and can be diazotized in soln. or 
on fiber. 


611,663—Oct. 4, 1898. Moritz Unricu, Germany. (Elberfeld.) 
Orange dye and process of making same. 


4-Amino azo BENZENE sulfo or other, coupled with nitro 3-PHENYLENE DIAMIN, or other nitro 
meta diamin of the benzene series. An ORANGE direct dye, fast to acids, alks., light. 


611,664—Oct. 4, 1808. Moritz Unricu, Germany. (Elberfeld.) 
Blue dye and process of making same. 


I-AMINO 8-NAPHTHOL 3.6-disulfo “H,” or other peri amino naphthol sulfo, coupled with 
phenyl 1-NAPHTHYLAMIN 8-sulfo, or homologs. A BLUE acid dye, fast to acids, alks., and light. 


613,638—Nov. 1, 1898. Karl Exper and Ignaz Rosenperc, Germany. (Kalle.) 
Primary disazo blue-black dye. (Process also claimed.) 
I-AMINO 8-NAPHTHOL 4.6-sulfo “K,’? coupled with diazo 1-NAPHTHYLAMIN, then with diazo 


ANILIN, both in acid soln. A sLack acid dye, fast to acids. 
S. 21s—“Blue Black N.” Ability to combine with both diazo salts in acid soln. is peculiar 


to “K” sulfo acid. 


ae ee ee ee ee eee ee Cee 


GROUP VI.—AZO II5 


613,639—Nov. 1, 1898. Karl Evsen and Ignaz Rosrenserc, Germany. (Kalle.) 
Primary disazo blue-black dye. (Process also claimed.) 

I-AMINO 8-NAPHTHOL 4.6-disulfo “K,” coupled with diazo 4-NITRANILIN and diazo ANILIN, 
both in acid soln. Brue to siack acid dye. 

Note 613,638 and 613,640. 


613,640—Nov. 1, 1808. Ignaz RosenserG and Karl ExseLt, Germany. (Kalle.) 
Greenish-blue polyazo dye. (Process also claimed.) 

I-AMINO 8-NAPHTHOL 4.6-disulfo “‘K,’’ coupled with diazo 1-NAPHTHYLAMIN, then with tetrazo 
BENZIDIN, and finally with 2-amINo 8-NAPHTHOL 6-sulfo ‘“‘G,” all in acid soln. 

Addition to 613,639. 


613,641—Nov. 1, 1808. Ignaz RosENnBERG and Friedrich Krecxse, Germany. (Kalle.) 
Greenish-blue mixed disazo dye. 

I-AMINO 8-NAPHTHOL 4.6-disulfo ‘‘K’’ coupled with tetrazo BENZIDIN, or other, and resulting 
intermediate coupled with 2-AMINO 8-NAPHTHOL 6-sulfo “G.” A BLUE to BLACK direct or developed 


(coupled) dye, that can be diazotized and coupled on fiber. 
Addition to 613,639. 


613,642—Nov. 1, 1808. Ignaz RosENBERG, Germany. (Kalle.) 
Deep-blue dye and process of making same. 

I-AMINO 8-NAPHTHOL 4.6-disulfo “K,”? combined with tetrazo BENZIDIN, then 1.3-NAPHTHALENE 
DIAMIN 6-sulfo added. A BLUE to BLACK direct and developed (coupled) dye, that can be diazo 
tized on fiber. 

Addition to 613,639. 


613,643—Nov. 1, 1808. Ignaz RosEnBERG and Bruno HeumMert, Germany. (Kalle.) 
Orange-brown polyazo dye. (Process also claimed.) 

I.3-NAPHTHALENE DIAMIN 6-sulfo, combined with diazo ANILIN, then with diazo BENZIDIN azo 
SALICYLIC acid, or other. 

Note 613,644, 45 and 46. 


613,644—Nov. 1, 1898. Ignaz RosgensBERG and Bruno HEeLmMert, Germany. (Kalle.) 
Reddish-brown polyazo dye. 
1.3-NAPHTHALENE DIAMIN 6-sulfo, combined with diazo 1-NAPHTHYLAMIN then with diazo BEN- 


ZIDIN azo SALICYLIC acid. A red-Brown direct dye. 
Addition to 612,643. 


613,645—Nov. 1, 1898. Ignaz RosENBEeRG, Germany. (Kalle.) 
Black polyazo dye. (Process also claimed.) 

I-AMINO 8-NAPHTHOL 4.6-disulfo “‘K,”? or acid ‘“H’’ combined with diazo 4-NITRANILIN, and 
after nitro group is reduced at 50-60° by Na,S combined with tetrazo BENzIDIN, or other, then 
in alk. soln. with 1.3-NAPHTHALENE DIAMIN 6-sulfo. A BLAcK direct dye that can be diazotized 
on fiber. 

- Addition to 613,643. 


613,646—WNov. 1, 1898. Ignaz RosENBERG and Friedrich KrecKr, Germany. (Kalle.) 
Substantive disazo dye. (Process also claimed.) 

To.ip1n, or other, coupled in alk. soln. with one mol. each of 2-aMINO 8-NAPHTHOL 6-sulfo 
“G” and 1.3-NAPHTHALENE DIAMIN 6-sulfo. A blue-vioLEt direct or developed dye that can be 
diazotized on fiber. 

Addition to 613,643. 


613,920—Nov. 8, 1898. H. Gutzxow, Germany. (Hochst.) 
Green-blue soluble dye and process of making same. 


as-Diethyl saFRANIN (by oxidation of amino diethyl anilin and anilin, 2 mols.) or homologs, 
coupled with 1-NAPHTHYLAMIN. A BLUE basic dye. 
Near S. 128—‘“‘Janus Gray B.” 


116 DIGEST OF PATENTS 


614,391—Nov. 15, 1898. Adolf Israz, and Richard Kotuz, Germany. (Elberfeld.) 
Disazo dye and process of making same. (Product only claimed.) 

Acetyl 4-NAPHTHYLENE DIAMIN, coupled in acid soln. with 1-NAPHTHYLAMIN 6-sulfo 
“Cleve’s,” again diazotized and coupled in alk. soln. with 2-NAPHTHOL 6-sulfo, then saponified by 
alk. <A gray to deep BLUE direct and developed dye, that can be coupled on fiber and is then fast 
to acids, alks., washing and light. 


615,497—Dec. 6, 1808. Christopher Ris and Charles Simon, Switzerland. (Geigy.) 
Black trisazo dye and process of making same, 


4-PHENYLENE DIAMIN, coupled with 1-AMINO 8-NAPHTHOL 5-sulfo, then tetrazotized and 
coupled with 1 mol. each of 3-PHENYLENE DIAMIN and RESORCIN. A BLACK direct dye. 
S. 437—‘“Isodiphenyl Black B.” 


617,544—Jan. 10, 1890. Franz Scuoit, Germany. (Héchst.) 
Yellow basic disazo dye and process of making same. 


Trimethyl ammonium 3-PHENYLENE DIAMIN coupled with 3-ToLUIDIN, again diazotized and 
coupled with aceto ACETANILID. A light YELLOW acid dye. 


617,963—Jan. 17. 1899. Harry Kircuuorr, Germany. (Berlin.) 
Red dye. 
2-Amino 4-CRESOL (OH = 1), methyl ether, coupled with NaputTHo1 sulfamino sulfo. <A 


violet RED acid dye. 


618,963—Feb. 7, 1899. Richard Taccrsett, New York. (Schoellkopf.) 
Blue-black azo dye and process of making same. 

SULFANILIC acid, metanilic acid or toluidin sulfo acid, etc., coupled with 1-NAPHTHYLAMIN, 
again diazotized and coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo “H’’? or “K” (1.8.4.6.) or 
(1.8.5.7). A blue-BLack acid dye, fast to washing, light. 

S. 261—‘‘Buffalo Black 10B.” 


619,194—Feb. 7, 1809. Ivan LrEviNstE1N and Richard Herz, England. (Levinstein.) 
Naphthylene-diamin-sulfonic acid and process of making same. _1.4-Diamino 
naphthalene 2-sulfo that oxidizes readily in acid or alk, soln. to yellow color with green fluor. 
ANILIN, homolog, or deriv., diazotized and coupled below 15° with 1-NAPHTHYLAMIN 2-Sulfo, 
then reduced with Fe and HCl, free anilin recovered by steam distn., soln. filt. and pptd. by 


HCl. Bracx direct dye. 
This patent is classed by Schulz under 461, “(Coumassie Union Black,” though intermediate 
only is claimed. 


619,503—Feb. 14, 1809. Christopher Ris, Switzerland. (Geigy.) 
Black trisazo dye and process of making same. 


ToLiDIN or acet 4-phenylene diamin, coupled with 2-AMINO 8-NAPHTHOL 6-sulfo, rediazotized 
and coupled with 1 mol. each of 3-TOLUYLENE DIAMIN sulfo and 3-PHENYLENE DIAMIN. Other 
combinations claimed. A deep BLACK direct dye. 


619,518—Feb. 14, 1899. Moritz Unricu, Germany. . (Elberfeld.) 
Yellow dye and process of making same. 


4-4'-Diamino DIBENZYL 3.3/-disulfo, coupled with 2 mols. nitro 3-PHENYLENE DIAMIN. A 
YELLOW direct dye, fast to alks. and acids. 


620,368—Feb. 28, 1899. Jakob Scumip, Switzerland. (Basle.) 


Blue tetrazo dye and process of making same. 

I-AMINO 8-NAPHTHOL 3.6-disulfo, or isomers, heated with acetic acid and acetic anhyd. to 
form 1.8-naphthacetol 3.6-disulfo, then boiled in dil. alk. soln., cooled, combined with tetrazo 
DIANISIDIN or other para diamin, and 1-NAPHTHOL 4-sulfo acid, or other. Buux direct dyes, not 


diazotizable on fiber. 
Near S. 428—‘‘Direct Blue B.”’ Note 620,369. 


a ee 


<a 


ore XR. 


GROUP VI.—AZO sie, 


620,369—Feb. 28, 1899. Jakob Scumip, Switzerland. (Basle.) 
Blue tetrazo dye and process of making same. 

TOLIDIN, or homolog, coupled with 1 mol. each of 1.8-NAPHTHACETOL 3.6-disulfo or other, 
and I-AMINO 8-NAPHTHOL 3.6-disulfo “‘H,’” or isomers. A BLUE direct dye, containing but one 
diazotizable group on fiber. 


620,574—Mar. 7, 1809. Karl Ex.sey and Julius Oppermann, Germany. (Kalle.) 
Black trisazo dye. (Process also claimed.) 

Chlor nitro BENzoIC acid, condensed with 4-PHENYLENE DIAMIN, reduced, coupled with 
2-AMINO 8-NAPHTHOL 6-sulfo “G,’’ diazotized and coupled with 2 mols. 3-TOLUYLENE DIAMIN, or 
other. A blue siack direct or developed dye, fast to washing and soap, that can be coupled on 
fiber or after treated with metals to render faster. 


622,961—Apr. 11, 18099. Ivan LevINnsTeEIN and Carl MENscHING, England. (Levinstein.) 
Brown tetrazo dye and process of making same. 

BENZIDIN, dianisidin, etc., coupled with 1 mol. each of saticyiic acid, or other ortho hydroxy 
carbo acid, and ANILIN, or homolog, rediazotized and coupled with 2-AMINO 8-NAPHTHOL 6-sulfo 
“G,”’ or homolog. Naphthol sulfo acids give red dyes and salicylic acid yellow. Brown, RED or 
YELLOW direct dyes, fast to light. 

S. 444—‘‘Crumpsell Direct Fast Brown B” and “C.” 


624,256—May 2, 1880. Karl ScHIRMACHER, Germany. (Hochst.) 
Red-brown monoazo dye and process of making same. 

Picramic acid, coupled with methyl 2-AMINO 5-NAPHTHOL 7-sulfo, or homologs. Brown to 
BLACK, acid and developed (CrO,) dyes. 


625,174—May 16, 1890. Ivan LeEvinsTEIN and Herman PFEIFFER, England. (Levinstein.) 
Substantive red tetrazo dye and process of making same. 


Dichlor diacet BENzIDIN, coupled with 2 mols. NAPHTHIONIC acid, or 2-naphthylamin 6-sulfo, 
“Broénner.” A violet RED direct dye, fast to organic acids. 
S. 350—‘‘Dianol Red 2 B.”’ 


625,198—May 16, 1899. Alfred Puitiips and Moritz von Gators, Germany. (Hdéchst.) 
Process of dyeing on fiber. 


Fiber* prepared with 2-NAPHTHOL mixture containing alkali, guni tragacanth and ammonium 
ricinoleate is printed with soln. of tetrazo dimethyl diamino carBazoL. Buacx developed dye. 


626,913—June 13, 1899. Ernst Konic, Germany. (Hochst.) 
Brown-yellow azo dye and process of making same. 

Trimethyl ammonium 3-PHENYLENE™DIAMIN, coupled with REsoRCIN. Brown YELLOW basic 
mordant dye, fast to light. 

S. 6o0—‘“‘Azophosphin GO” and S. 435—‘“Janus Brown B.” Note 602,638-39 and 40, 
610,435 and 623,697. 


626,935—June 13, 1899. Franz Scuott and Arnold Hess, Germany. (Hoéchst.) 
Disazo dye and process of making same. 

Amino benzyl] pyripin chloride from nitro product, coupled with 3-TOLUIDIN or other amin, 
rediazotized, and coupled with 2-NAPHTHOL, or other. Vari-colored basic mordant dye. 


627,679—June 27, 18909. Melchior BonicErR and Jan Lacurt, Switzerland. (Sandoz.) 
Green trisazo dye and process of making same. 

I-AMINO 8-NAPHTHOL 3.6-disulfo ““H’’ coupled with diazo 2.4 or 2.5-dichlor ANILIN, then with 
tetrazo BENzIDIN, followed by PHENOL, salicylic acid, etc., all in alk. soln. Grern direct dye, 


fast to light and carbonates. 
S. 470—“Chloramin Green B.” Note 514,599, 585,104 and 652,456. 


627,783—June 27, 1809. Karl ScurrRMACHER, Germany. (Hochst.) 
Black azo dye and process of making same. 

Picramic acid, coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo ““H,” or other. Brack to deep 
GREEN acid and developed (CrO,) dye, fast to washing, soap and fulling. 


*Though presented as application patent, the dye is new. Note Ser. 669,239. 


118 DIGEST OF PATENTS 


628,025—July 4, 1899. Carl OrLscHLAEGEL, Germany. (Berlin.) 
Blue-black wool-dye and process of making same. 
4’-Amino 2/-sulfo phenyl 2-NAPHTHYLAMIN, coupled with 1-NAPHTHYLAMIN in acetic soln., 


then recoupled in alk. soln. with 2-napHTuHoL 6-sulfo. Other components claimed. Blue-sracx 
acid dye, fast to light and milling. 


628,233—July 4, 1899. Charles Simon, Switzerland. (Geigy.) 
Green trisazo dye and process of making same. 

2-Chlor 4-NITRANILIN, dissolved in conc. H,SO,, diluted, and coupled with 1-am1no 8-NAPH- 
THOL 3.6-disulfo “H,” then with tetrazo BENzIDIN, and finally with PHENOL, or other. GrREEW 


direct dye, fast to acids, light and soap. 
Near S. 474—‘“Diamin Green B.” 


628,721—July 11, 1899. Carl O. Miier, Switzerland. (Durand.) 
Blue-black dye and process of making same. 

Acet 4-PHENYLENE DIAMIN, or nitro comp., coupled with saLicynic acid, or other, saponified 
or reduced, rediazotized, and coupled with 1.8-dioxy NAPHTHALENE 4-sulfo. Blue-stacKx acid 
mordant dye, fast to light and fulling. 


628,814—July 11, 1889. Paul Jutius, Germany. (Badische.) 
Brown 220 dye. 

2-Nitro 6-AMINO PHENOL 4-sulfo, or (4.2.6) comp., coupled with 3-PHENYLENE DIAMIN. BROWN 
acid and developed dye, fast as alizarin colors—resists milling, washing, rubbing, carbonizing, 


steam, SO, and light. 
Near S. 154—‘‘Acid Alizarin Brown B.” 


629,748—July 25, 1899. Ivan L&vinstE1In and Richard Herz, England. (Levinstein.) 
Blue-black disazo color and process of making same. 

Acetyl 1.4-NAPHTHALENE DIAMIN 5- or 7-sulfo, coupled with 1-NAPHTHYLAMIN rediazotized 
and coupled in alk. soln. with 2-amMINo 8-NAPHTHOL 6-sulfo “Gamma” and saponified in dil. NaOH 
at 90°. Other components claimed. Blue-sLnack and sLuk direct and developed dyes, fast to 
milling, light, and can be coupled on fiber. 

S. 274—‘‘Diaminogen B.” Note 533,463 and 560,796. 


631,0S89—Aug. 15, 1899. Paul O. Mutuer, Switzerland. (Durand.) 
Red dye and process of making same. 

Acet. 4-PHENYLENE DIAMIN, coupled with saLicyzic acid and 1-NAPHTHOL 4-sulfo “NW.” 
Other components claimed. Rep to blue-BLacx acid mordant dye, fast to light and fulling. 

S. 291—‘‘Azo Alizarin Bordeaux W.” 


631,610—Aug. 22, 1899. Heinrich A. BERNTHSEN and Paul Jutius, Germany. (Badische.) 


Orange dye and process of making same. 

BEnzipIn, or other, coupled with 3-PHENYLENE DIAMIN disulfo, filt., made into paste, and 
coupled with nitro 3-PHENYLENE DIAMIN. ORANGE direct and developed dye, fast to washing, 
acids and light, when after treated with diazo 4-nitranilin dyeings are browner. 

S. 306—“Pyramin Orange.” Note 631,611. 


631,611—Aug. 22, 1899. Heinrich A. BERNTHSEN and Paul Junius, Germany. (Badische.) 


Disazo orange dye and process of making same. 
Benzipin, or other, coupled with 2-NAPHTHYLAMIN 3.6-disulfo “‘Amino R-acid,” or “Amino F 
acid’? (2.3.7), then with nitro 3-PHENYLENE DIAMIN. Red orancg direct dye, fast to light, acids 


and Cl. 
S. 314—“Pyramin Orange 2R.” Addition to 631,610. 


682,503—Sept. 5, 1899. Alfred Puizips, Germany. (Hoéchst.) 


Process of dyeing. 

Fabric is prepared with 2-NAPHTHOL grounding containing NaOH and sod. ricinoleate and 
printed or dyed with a comp. containing tetrazotized diamino CARBAZOLE and the usual thickening 
and neutralizing agents. Brown to brown sLack developed dyes, faster to light when coppered. 
The meta carbazol yields a yellow-brown tint and the para comp. deep brown black. 


' 
§ 
: 
; 


GROUP VI.—AZO 119 


634,009—Oct. 3, 1899. Ivan LevenstTeEIN and Richard Herz, England. (Levinstein.) 
Blue-black tetrazo dye and process of making same. 
1.4-NAPHTHALENE DIAMIN 2-sulfo,* coupled with 1 mol. each of 2-NAPHTHOL, 3.6-disulfo ‘“R” 


and 2-NAPHTHOL. Other components claimed. Brug and siacx acid and direct dyes. 
*For mfr. of sulfo acid see Intermediate, same group. Also note 629,748. 


634,824—Oct. 10, 1889. Paul Junius and Richard Larstin, Germany. (Badische.) 
Dyeing wool fast black. Dyeing wool fast black with disazo dyes from 2-amino phenol 
4-sulfo. 


Wool fiber dyed with 2-amino PHENOL 4-sulfo azo I1-NAPHTHYLAMIN azO 2-NAPHTHOL 6-sulfo, 
or similar dye, using bisulfite and acetic acid, then boiled with bichromate. Blue-sLacK to 
green-BLAcK direct and developed (CrO,) dyes. 


638,127—Nov 28, 1899. Georg Koerner, Germany. (Badische.) 
Black azo dye. 

4-PHENYLENE DIAMIN aZO 3-PHENYLENE DIAMIN, or Other, coupled with 1-AMINO 8-NAPHTIOI, 
4- or 5-sulfo in acetic acid soln. and with 4-PHENYLENE DIAMIN azo SALICYLIC acid in alk., neut. 
or weak acid soln., or other (see list and restrictions). Buacx direct dyes. 

Basic diazo-azo residue is attached near NH, group and hydroxy diazo-azo comp. near OH. 


639,040—Dec. 12, 1899. Julius Hrerspaspny and Christoph Hartmann, Germany. 
Green-blue tetrazo dye. 

2.6-TOLUYLENE DIAMIN 4-sulfo, or other, coupled in weak alk. soln. with 2 mols. diazo 4-n1- 
TRANILIN, reduced with Na,S at 50-90°, pptd. by acid, purified, tetrazotized, and coupled with 
2 mols. I-AMINO 8-NAPHTHOL 3.6-disulfo ‘‘H.”’ 

Note 639,041. 


639,041—Dec. 12, 1899. Julius Herspapny and Christoph Hartmann, Germany. 
Black tetrazo dye. 

3-TOLUYLENE DIAMIN, coupled with 2 mols. diazo 4-NITRANILIN, reduced (Na,$), diazotized, 
and coupled with 2 mols. 2-AMINO 8-NAPHTHOL 6-sulfo ‘‘G.”? Buxracxk acid or direct dye, fast 
to washing. 

Addition to 639,040. 


639,042—Dec. 12, 1899. Julius Herpasny, Germany. (Oehler.) 
Claret-red tetrazo dye. (Process also claimed.) 


ToLipiIn, or other, coupled with 2 mols. amino 1-phenyl PYRAZzOLONE 3-carbo. Rep direct and 
developed dye, fast to light, washing, soap, and can be diazotized and coupled on fiber. 


640,010—Dec. 26, 1889. Carl O. MuLuErR, Switzerland. (Durand.) 
Blue-black dye. 

4-PHENYLENE DIAMIN and salicylic acid (by reduction of 4-nitranilin azo salicylic acid or 
saponification of acet 4-phenylene diamin azo salicylic) or other, coupled with 1.8-dioxy NAPH- 


THALENE 3.6-disulfo. Blue-pLacx acid mordant dye, fast to light and fulling. 
S. 292—‘‘Azo Alizarin Black I.” 


640,989—Jan. 9, 1900. M. Bonicer, Basle, Switzerland. (Sandoz.) 
Bluish-red azo dye. 

Ditolyl 1-sulfamino 8-nAPHTHOL 3.6-disulfo (or 1.8.2.4 or 1.8.4.6 deriv.) in dil. alk. carb. 
soln. below 5° combined with diazo. ANILIN or other. A violet-rED acid dye, fast to acids, 
alks., light. 

S. 182—‘Fast Sulfon Violet 5BS.” 


644,233—Feb. 27, 1900. P. Junius, Germany. (Badische.) 
Black disazo dye. 

2-Nitro 6-amino PHENOL 4-sulfo coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo again diazotized 
and coupled with 1-NAPHTHOL 4- or 5-sulfo or other. A BLUE to BLACK, direct and developed 
(CrO,) dye, fast to light and when chromed fast to fulling. 

Note 644,234 to -40. 


120 DIGEST OF PATENTS 


644,234—Feb. 27, 1900. P. Junius, Germany. (Badische.) 
Black dye. 


2-Nitro 6-amino PHENOL 4-sulfo coupled with 1-NAPHTHYLAMIN, again diazotized and coupled 
with I-NAPHTHYLAMIN. Dye may be reduced with (NH,),S in stages and when completely 
reduced the first component coupled with R salt gives a blue that turns red with HCl. A sBriack 
acid mordant dye. 


Addition to 644,233. 


644,235—Feb. 27, 1900. P. Juuius, Germany. (Badische.) 
Black disazo dye. 


2-Nitro 4-amino PHENOL 6-sulfo acid coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo, ‘‘Cleves” 
again diazotized and coupled with 1-NAPHTHOL 4- or 5-sulfo acid or other. Note test of dye 
reduced by (NH.) S in stages as in 644,234. A blue or green siacKk direct and developed 
(CrO,) dye, fast to light and when chromed fast to washing and fulling, and greener. 


Addition to 644,233. 


644,236—Feb. 27, 1900. P. Juuius, Germany. (Badische.) 
Black disazo dye. 


4-Nitro 2-amino PHENOL 6-sulfo coupled with 1-NAPHTHYLAMIN Of I-NAPHTHYLAMIN 6- or 
7-sulfo ‘Cleves’? again diazotized and coupled with I-NAPHTHYLAMIN 4- or 5-sulfo. Note test 
of reduced dye. A blue or green Biack direct and developed (CrO,) dye, fast to light, and 
when chromed fast to washing, fulling and greener. 


Addition to 644,233. 


644,237—Feb. 27, 1900. P. Junius, Germany. (Badische.) 
Black dye. 


2-Nitro 6-amino PHENOL 4-sulfo coupled with 1-NAPHTHYLAMIN, again diazotized and coupled 
with 2-NAPHTHOL. A BLUE and BLAcK direct and developed (CrO,) dye. 


Addition to 644,233. 


644,238—Feb. 27, 1900. P. Jutius, Germany. (Badische.) 
Disazo dye from chloramidophenol. 


4-Chlor 2-amino PHENOL coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo “Cleves” or other, 
again diazotized and coupled with 1-NAPHTHYLAMIN, or other. A BLUE to violet BLAck direct and 
developed (CrO,) dye, fast to light, and when chromed faster to light and greener. 


Addition to 644,237. 


644,239—Feb. 27, 1900. P. Junius, Germany. (Badische.) 
Black disazo dye. 


2-Chlor 6-amino PHENOL 4-sulfo coupled with 1-NAPHTHYLAMIN, or other, again diazotized 
and coupled with 2-NAPHTHOL 3.6-disulfo “R.’? A siacK direct and developed (CrO,), fast to 
light and when chromed fast to milling and washing. 


Addition to 644,233. 


644,240—Feb. 27, 1900. H. A. Berntusen, and P. Junius, Germany. (Badische.) 


Black disazo dye. 
4-Nitro 2-amino PHENOL coupled with 1-NAPHTHYLAMIN and again coupled with 1.8-dioxy 
NAPHTHALENE 4-sulfo. Other components are claimed. A blue to green BLacK, acid and de- 
veloped (CrO,) dye. 
Addition to 644,233. 


644,291—Feb. 27, 1900. J. Hersasny, Germany. (Oehler.) 


Black trisazo dye. 

2-AMINO 8-NAPHTHOL 6-sulfo “G’” coupled with 2.6-roLUYLENE DIAMIN 4-sulfo (or 2.4.6.) 
then combined in strong alk. soln. with one equivalent of tetrazo BENZIDIN, or other, and product 
coupled with 2-amINno 8-NAPHTHOL 6-sulfo ‘‘G.” Other components claimed. Brack direct dyes, 
fast to soap, give white discharge, and will diazotize and develop on fiber. © 


ee Oe ee a ee, ee ere 


| 
j 
. 
. 


GROUP VI.—AZO I21I 


644,292—Feb. 27, 1900. J. Herpasny, Germany. (Ochler.) 
Black polyazo dye. 

BENZIDIN, or other, coupled with 2 mols. azo dye 2-AMINo 8-NAPHTHOL 6-sulfo “G” azo 
2.6-TOLUYLENE DIAMIN 4-sulfo (or 2.4.6) or other. A BLacK direct dye, even, fast to soap, dis- 
charges white, and can be diazotized on fiber. 

Near S. 491—“‘Dianil Black PR.” Addition to 644,291. 


644,334—Feb. 27, 1900. C. Scurause and E. Scuiricuer, Germany. (Badische.) 
Black trisazo dye. 


SuLFANILIC acid coupled in acid soln. with 1-AMINo 8-NAPHTHOL 4-sulfo then combined 
with diazo amino azo BENZENE, or other in alk. soln. A sLack acid dye, fast to light. 


644,462—Feb. 27, 1900. | C. Ris, Switzerland. (Geigy.) 
Disazo dye from stilbene. 

4-Nitro TOLUENE sulfo condensed with 4-PHENYLENE DIAMIN or other then diazotized’ and 
coupled with PHENOL and product heated in autoclave to 100-1109 with gray. chloride or 
bromide. Third component may be 2-AMINO 8-NAPHTHOL 6-sulfo or derivs. An ORANGE or BROWN 
direct dye, fast to light, alks. and acids. 

S. 205—“Diphenyl Chrysoin RR,” S. 206—“Diphenyl Catechin G,” and S. 207—‘‘Dipheny]l 
Fast Brown G.” Note that these are also stilbene dyes though classed by Schulz among azo. 


646,711—Apr. 3, 1900. O. Soust, Germany. (Hochst.) 
Black azo dye and process of making same. 


Picramic acid coupled in alk. soln. with acetyl 1-aMINO 8-NAPHTHOL 3.6-disulfo (or 1.8.4.6). 
A sBLack and olive GrEEN (Cr) acid dye, faster than nonacetylated dye. 


647,236—Apr. 10, 1900. K. ScurrMacHER, Germany. (Héchst.) 
Brown dye and process of making same. 
3-Nitro 2-amino PHENOL 5-sulfo (or 5.2.3) coupled with 3-PHENYLENE DIAMIN, homologs 


or sulfo acids. A Brown acid and developed (CrO,) dye, faster when chromed. 
Near S. 154—‘‘Acid Alizarin Brown B.”’ 


647,237—Apr. 10, 1900. F. Scumipt, Germany. (Héchst.) 
Diamidodiphenylamin sulfonic acid and process of making same. 
4.4’-Diamino DIPHENYLAMIN 2.2’-disulfo coupled in alk. soln. with 2 mols. 2-AMINO 8-NAPH- 
THOL 6-sulfo “‘G,”’ recoupled with 2 mols. 3-PHENYLENE DIAMIN. If first coupler is 3-phenylene 
diamin and second is diazo 4-NITRANILIN (coupled on fiber) the color is violet then brown, 
Other components claimed. A sLack to BROWN direct dye. 
Dyes not claimed though given in examples. 


648,623—May 1, 1900. A. IsrazL and R. Korusr, Germany. (Elberfeld.) 
Blue trisazo dye. 

Acetyl 4-PHENYLENE DIAMIN coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo “‘Cleves’’ diazotized 
and coupled again with Cleves acid, again diazotized and coupled with 2-NaPHTHOL 6-sulfo then 
saponified. A sLur direct dye, fast to washing, especially to light and can be diazotized on 
fiber, etc. 

Note 658,897. 


649,727—May 15, 1900. B. Homouixka, Germany. (Hochst.) 
Blue basic dye and process of making same. 


as-Diethyl pheno-sAFRANIN, or other 2 mols., coupled with 2-napHTHOL in alk. soln. A BLUE 
basic dye. 
Note 524,252 and 649,728 for dye from equi-molecular proportions of above. 


649,728—May 15, 1900. B. Homoixa, Germany. (Hochst.) 
Blue basic dye and process of making same. 


SAFRANIN or pheno-safranin, 2 mols., coupled with 2-NAPHTHOL, in neutral, slightly acid or 
NH, soln. Buus basic dyes. 
Addition to 649,727. 


122 DIGEST OF PATENTS 


650,757—May 29, 1900. P. Junius, Germany. (Badische.) 
Azo dye for lakes. 
2-NAPHTHALAMIN 1-sulfo coupled with 2-NAPHTHOL, pptd. on a metallic base. A RED dye 


for lakes, fast to acids, light, will not sublime. 
S. 173—‘‘Lithol Red R.” 


652,456—June 26, 1900. M. Bonicrer and J. Lacurr, Switzerland. (Basle.) 
Blue trisazo dye and process of making same. 

2.5-Dichlor ANILIN or other, coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo then combined 
with one equivalent tetrazo BENZIDIN in alk. soln. and finally coupled with a second mol. of 
I-AMINO 8-NAPHTHOL 3.6-disulfo. Other components claimed. A green to dark BLUE, direct or 
acid dye. 

S. 471—‘‘Chloramin Blue 3 G.” 


654,064—July 17, 1900. P. Junius, Germany. (Badische.) 
Blue monoazo dye. 

6-Nitro 2-amino PHENOL 4-sulfo coupled with 1-AMINO 5-NAPHTHOL 7-sulfo. A BLUE to 
darker (Cr) acid and acid mordant dye, which when chromed is fast to light, milling, wash- 
ing, etc. 

Near S. 159—‘‘Acid Alizarin Black R.’? Note 644,233, 667,935 and 654,065. 


654,065—July 17, 1900. P. Jurius, Germany. (Badische.) 
Blue-violet monoazo dye. 

6-Nitro 2-amino PHENOL 4-sulfo coupled with 2-AmMINo 8-NAPHTHOL 6-sulfo “G.” <A _ blue- 
VIOLET and siacK (Cr) acid and acid mordant dye, which after chroming is fast to light, mill- 


ing, washing, etc. 
Near S. 159—‘“‘Acid Alizarin Black R.”? Addition to 654,064. 


654,167—July 24, 1900. I. LevinsteEIn and C. Menscuinc, England. (Levinstein.) 
Black azo dye and process of making same. 


Acetyl 4-PHENYLENE DIAMIN €azZO I-NAPHTHYLAMIN coupled with 2-NAPHTHOL 3.6-disulfo “‘R’” 
then saponified. A sack acid dye. 

S. 243—‘‘Coomassie Wool Black R’” and S. 244—‘‘Coomassie Wool Black S.” Note 
654,168. 


654,168—July 24, 1900 I. Levinstein and C. Menscuinc, England. (Levinstein.) 
Black azo dye and process of making same. 

Acetyl 4-PHENYLENE DIAMIN aZO I-NAPHTHYLAMIN coupled with 2-NAPHTHOL 6-sulfo 
“‘Schaeffer’’ or similar acid. A red to blue BLacK acid or direct dye. 


S. 243—‘‘Coomassie Wool Black R,’? and S. 244—‘‘Coomassie Wool Black S$.” Addition 
to 654,167. 


655,013—July 31, 1900. C. Ris and C. Simon, Switzerland. (Basle.) 
Process of making green trisazo dyes. (Product also claimed.) 


2-Chlor anilin coupled in neut. soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo, next combined 
with diazo BENZIDIN in alk. carb. soln., then with PHENOL in alk. soln. and mixture heated to 
90°. GREEN direct dyes. 


655,529—Aug. 7, 1900. Joseph Turner, England. 
Amidosulfonic acid. 


Amino sulfo saticyLic acid, 2-amino phenol sulfo, or other, coupled with 1-NAPHTHYLAMIN, 
or other, again diazotized and coupled in alk. carb. soln. with 2-naphthol 3.6-disulfo acid R, or 
other. BLAcK, VIOLET or BROWN acid and acid mordant dyes, suitable for lakes. No claims for 
dyes, though these are given as examples of patent. 


656,619—Aug. 28, 1900. J. Bammann and E. Davipis, Germany. (Elberfeld.) 
Blue tetrazo dye and process of making same. 


BeEnzIpIN, or other, coupled with 1 mol. each of 1-NAPHTHOL 3.6-disulfo and 2-AMINO 7-NAPH- 
gHoL. A red vIOLET to BLUE direct and developed (coupled) dye, that can be coupled on fiber. 


GROUP VI.—AZO 123 


656,620—Aug. 28, 1900. J. Bammann, E. Davinis, and W. VorstER, Germany, (Elberfeld.) 
Blue-red substantive dye. 

2.6-xYLIDIN (NH, = 1), 2 mols.,,coupled in alk. soln. with 5.5’-dioxy 2-DINAPHTHYLAMIN 
7.7/-disulfo. A violet-rEp direct fast dye. 

Note 656,621. 


656,621—Aug. 28, 1900. J. Bammann, E.Dayinis, and W. VorstER, Germany. (Elberfeld.) 
Azo dyestufi and method of making same. 
ANILIN, 2 mols., or other, coupled in alk. soln. with 5.5/-dioxy 2-DINAPHTHYLAMIN 7.7/- 


disulfo. Mixed amino components claimed. Rep to BLUE direct fast dyes. 
Addition to 656,620. 


657,064—Aug. 28, 1900. W. HeErzperc and O. HANsMANN, Germany. (Berlin.) 
Brown dye. 
Picramic acid coupled with 4-chlor 3-PHENYLENE DIAMIN. A BROWN acid mordant (Cr) dye, 


fast to milling and light. 
S. 8 9—“Metachrome Brown B.” Note 657,065, 658,506 and 7. 


657,065—Aug. 28, 1900. W. Herzperc and O. Hansmann, Germany. (Berlin.) 
Reddish-brown dye. 
Picramic acid coupled with 5-chlor 3-PHENYLENE DIAMIN. A red-BRowNn acid mordant 


(Cr) dye. 
S. 8 9—‘“‘Metachrome Brown B.” Addition to 657,064. 


656,120—Aug. 14, 1900. . P. Junius, Germany. (Badische.) 
Yellow azo dye and process of making same. 
PRIMULIN or other thiazol coupled with nitro 3-PHENYLENE DIAMIN sulfo. A YELLOW direct 


dye, fast to chlorin. 
Near S. 191—‘‘Pyramin Yellow R.’’ 


658,506—Sept. 25, 1900. P. Ort, A. Isragt, and R. Korner, Germany. (Elberfeld.) 
Brown dye and process of making same. 

Prcramic acid coupled with amino PHENYL glycin sulfo, from 3-PHENYLENE DIAMIN Ssulfo 
acid, or other, and chlor acrric acid. A red to deep Brown acid and developed (CrO,) dye, 
which when chromed is fast to milling and light. 

Addition to 637,064. 


658,507—Sept. 25, 1900. P. Orr and F. VoucEer, Germany. (Elberfeld.) 


Brown azo dye and process of making same. 

Picramic acid coupled with methyl 3-PHENYLENE DIAMIN sulfo, or other, derived from 
METHYL iodide and 3-PHENYLENE DIAMIN sulfo. A red to deep Brown acid and developed (CrO,) 
dye which when chromed is fast to milling and light. 

Near S. 69—‘“‘Metachrome Brown B.’’. Addition to 657,064. 


658,897—Oct. 2, 1900. A. IsraEL and R. Korust, Germany. (Elberfeld.) 


Blue trisazo dye. j 

Acetyl 4-PHENYLENE DIAMIN, or other, coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo “Cleves” 
rediazotized and coupled with a second mol. of same, again diazotized and coupled with 2-amino 
3-NAPHTHOL 7-sulfo, or other. A violet-sLUE to green-BLUE direct dye, fast to light. 

Addition to 648,623. ; 


662,122——Nov. 20, 1900. A. Israey and R. Kotue, Germany, (Elberfeld.) 


Blue-red azo dye and process of making same. 

ANILIN, or other, coupled in acetic soln. with 5.5/-dioxy 7.7’-disulfo 2-DINAPHTHYL urea 
or thio deriv. which is produced from 2-AMINO 5-NAPHTHOL 7-sulfo and PHOSGENE, and the product 
combined with diazotized acetyl 4-PHENYLENE DIAMIN in alk. soln. A RED to ORANGE direct dye, 


fast to acids and light. 
S. 279—‘“‘Benzo Fast Scarlet.” Note 663,498. 


124 DIGEST OF PATENTS 


663,498—Dec. 11, 1900. A. Isragn and R Korue, Germany. (Elberfeld.) 
Orange azo dye and process of making same. 


ANILIN or other, 2 mols. coupled with dioxy disulfo 2-DINAPHTHYLAMIN urea derived from 
2-AMINO 5-NAPHTHOL 7-sulfo and PHOSGENE, or thio deriv. An orange yELLow to violet RED 


direct dye, fast to acids and light. 
S. 279—‘‘Benzo Fast Scarlet.” Addition to 662,122. 


664,955—Jan. 1, 1901. F. Krecxre, Germany. (Kalle.) 
Monoazo black dye and process of making same. 


Pricramic acid coupled with 1.6-dioxy NAPHTHALENE 3-sulfo. A vio_ET and BLACK acid and 
developed (CrO;) dye which when chromed is fast to alks., soap, and light. 
Near S. g1—‘‘Anthracyl Chrome Green.” 


665,696—Jan. 8, 1901. K. Scuirmacuer, Germany. (Hochst.) 
Wool dye and process of making same. 


2.6-Diamino PHENOL 4-sulfo, derived from dinitro product, tetrazotized and coupled with 
2-NAPHTHOL. Combining weight given in patent shows but one mol. of naphthol, when the 
NaNO, used is sufficient for tetrazo comp. A BRown to violet-BLacK direct and developed (CrO,) 


fast dye. 
S. 288—‘‘Acid Alizarin Black SE.” Note 677,231, for closely related dye. 


666,866—Jan. 29, 1901. J. Hersasny, Germany. (Oehler.) 


Blue cotton dye and process of making same. 


Dianisip1n coupled in strong alk. soln. with 1 mol. each of diazo 2-AMINO 8-NAPHTHOL 
6-sulfo sulfurus acid salt, and’ 1-AMINO 8-NAPHTHOL 3.6-disulfo. Other components claimed. A 
BLUE direct dye, fast to light and washing. 


666,867—Jan. 29, 1901. J. Herspasny, Germany. (Oehler.) 
Claret-red disazo dye and process of making same. 


BENZIDIN coupled with 1 mol. each of saLicyLic acid and acetyl 2-AMINO 5-NAPHTHOL 7-sulfo. 


Other components claimed. A rep direct dye, fast to light and washing. 
S. 346—‘‘Oxamin Red.” This patent is apparently a duplication of 555,359 (Bernthsen 


and Julius). 
667,935—Feb. 12, 1901. O. Ernst and K. ScHIRMACHER, Germany (Hochst.) 


Violet-black aze dye and process of making same. 


6-Nitro 2-amino PHENOL 4-sulfo coupled with 2-NaPpHTHOL. A BLACK acid dye. 
S. 150—‘‘Acid Alizarin Black R.” Note 672,714, 644,233, etc., and 654,064 and -5. (Julius.) 


670,398—Mar. 19, 1901. J. Herpasny, Germany. (Oehler.) 


Blue triazol dye and process of making same. 
To.LipIN, or other, coupled with 1 mol. each of 1-AMINO 8-NAPHTHOL 3.6-disulfo and 4’-sulfo 
phenyl 3.6-dioxy 1.2-NAPHTHYL triazole. A BLUE direct dye, fast to washing. 


671,543—Apr. 9, 1901. K. Exset and I. Rosgenserc, Germany. (Kalle.) 


Black trisazo dye and process of making same. 
4.4/-Diamino DIPHENLAMIN coupled with 2-AMINO 8-NAPHTHOL 6-sulfo “Gamma” again d1azo- 
tized and coupled with 1 mol. each of 3-roLUYLENE DIAMIN and 1.3-NAPHTHALENE DIAMIN 6-sulfo. 


A BLACK direct dye. : 


671,896—Apr. 9, 1901. E. ScHiercuer, Germany. (Badische.) 


Violet dye. 
I-AMINO 8-NAPHTHOL 4- or 5.7-disulfo, that is, with a sulfo group in para and another in 7 
position, coupled with 1-NAPHTHYLAMIN.. A vIOLET acid or direct dye, fast to alks. and light. 


671,902—Apr. 9, 1901. A. Txatscu, Germany. (Badische.) 


Azo dye. 

2-Nitro 6-amino PHENOL 4-sulfo coupled with puHENyL glycocol sulfo, IV, from amino PHENOL 
sulfo IV, (D. P. 70,788) condensed with chlor acetic acid. A Brown and rep acid and developed 
(CrO,) dye, which when chromed is fast to milling and washing. 


GROUP VI.—AZO 125 


671,903—Apr. 9, 1901. A. Txatscu, Germany. (Badische.) 
Brown azo dye. 


2-Nitro 6-amino PHENOL 4-sulfo coupled with pHENnyL glycocol sulfo III, from amino pHENoL 
sulfo acid III (D. P. 74,111) condensed with chlor acetic acid. A Brown acid and developed 
(CrO,) dye, which when chromed is fast to milling and will not bleed. 

Addition to 671,902. 


671,904—Apr. 9, 1901. A. Txatscu, Germany. (Badische.) 
Brown azo dye. 


Picramic acid coupled with PHENYL glycocol sulfo IV, from amino pHENoL sulfo IV (D. P. 
70,788) condensed with chlor acrtic acid. A red to dark Brown acid and developed (CrO,) dye, 
which when chromed is fast to milling, washing and light. 

Addition to 671,902. 


672,714—Apr. 23, I9o01. K. ScHIRMACHER, Germany. (Hochst.) 
Wool-dye and process of making same. 


4-Chlor 2-amino PHENOL 6-sulfo coupled with 2-amino 8-NAPHTHOL 6-sulfo “G.”’ A red-BROWN 
to blue-cray acid and developed (CrO,) dye, which when chromed is fast to milling and light. 
Near S. 159—‘‘Acid Alizarin Black R.’? Addition to 667,935. 


673,079—Apr. 30, 1901. F. Herwic, Germany. (Elberfeld.) 
Disazo dye and process of making same. 

ANILIN, coupled in alk. soln. with 2-aMINO 5-NAPHTHOL 7-sulfo rediazotized and coupled in 
alk. soln. with 2-AMINO 5-NAPHTHOL 7-sulfo. Other components claimed. A rep to BLACK direct 
dye, fast to light and acids. 


675,629—June 4, 1901. A. IsrageL and R. Kotuer, Germany. (Elberfeld.) 
Azo dye. 4 


2-ANISIDIN, 2 mols., or other para diamin, coupled with 5.8/-dioxy 7.6’-disulfo 2-DINAPHTHYL 
tirea or other, prepared as in 675,627 among Intermediates. Corresponding thio urea and mixed 
diazo components'claimed. A RED to ORANGE direct dye, fast to acids and light. 


675,632—June 4, 1901. A. IsrageL and R. Korur, Germany. (Elberfeld.) 
Azo dye. 

4-TOLUIDIN, 2 mols., or other, coupled with 5.5’-dioxy 7.7/-disulfo 1.2-DINAPHTHYL urea. Cor- 
responding thio compound also claimed. An oRANGE to violet-rRED direct dye, fast to acids and 
light. 

Note 656,646 among Intermediates. 


676,494—June 18, 1901. H. Gre.permann, Germany. (Berlin.) 
Black disazo dye. 
s-Nitro 2-amino 4-crEso. (OH = 1) coupled in alk. soln. with 1-NAPHTHYLAMIN 6-sulfo, re- 


diazotized and coupled in alk. soln. with 2-am1no 8-NAPHTHOL 6-sulfo then reduced by Na,S. 
Other components claimed. A blue-snacKk direct and developed dye, fast when coupled on fiber 
with 3-phenylene diamin. 


676,495—June 18, 1901. Hugo GELDERMANN,Germany (Berlin.) 


Blue disazo dye. 

s-Nitro 2-amino 4-crEso. (OH = 1), methyl ether, coupled with 1-NAPHTHYLAMIN 6-sulfo, or 
other, rediazotized and coupled with 2-napHTHoL 6-sulfo, then reduced with Na,S in alk. soln. 
Vio.er and sive direct and developed (coupled) dyes that can be coupled on fiber with 2-naphthol. 


677,227—Tune 25, 1901. Paul Junius, Germany. (Badische.) 


Disazo dye. 

6-Nitro 2-amino PHENOL 4-sulfo, reduced to diamino compound, coupled with 1 mol. each 
of 2-NAPHTHOL 3.6-disulfo “R,’’ and 2-NAPHTHOL, or other. VuioLEet to green-BLUE acid and de- 
veloped (CrO,) dyes which when chromed are fast to milling, washing, light, steam and car- 
bonizing. 

S. 289—‘‘Acid Alizarin Black SN.” Note 680,183, 677,228 to 31, 644,233 to 40, 677,228 
to 31. 


126 DIGEST OF PATENTS 


677,228—June 25, 1901. Paul Junius, Germany. (Badische.) 
Disazo dye. 

6-Nitro 2-amino PHENOL 4-sulfo, reduced to diamino, coupled with 2-NaPH?THOL 6-sulfo and 
2-NAPHTHOL, or other. VIOLET to green-BLUE acid and developed (CrO,) ‘dyes which when 
chromed are fast to milling, washing, light, steam and :carbonizing. 

Addition to 677,227. 


677,229—June 25, 1901. Paul Junius, Germany. (Badische.) 
Disazo dye. 

6-Nitro 2-amino PHENOL 4-Sulfo, reduced, tetrazotized,and coupled with 2-NAPHTHOL, or 
other, and 2.7-dioxy NAPHTHALENE. VIOLET to green-BLUE acid and developed (CrO,) dyes which 
when chromed are fast to milling, washing, light, steaming, and carbonizing. 

Addition to 677,227. 


677,230—June 25, 1901. Paul Junius, Germany. (Badische.) 
Disazo dye. 

6-Nitro 2-amino PHENOL 4-sulfo, reduced, tetrazotized, and coupled with 2-NAPHTHOL and 
2-OXY NAPHTHOIC acid. VIOLET to green-BLUE acid and developed (CrO,) dyes which when 
chromed are fast to milling, washing, light, steaming, and carbonizing. 

Addition to 677,227. 


677,231—June 25, 1901. Paul Jutius, Germany. (Badische.) 
Disazo dye. 

2.6-Diamino PHENOL 4-sulfo, tetrazotized and coupled with 2 mols. 2-NAPHTHOL. ‘This looks 
to be same dye as 665,696, though proportion of 2-naphthol is different. The amount of NaNO, 
in both patents is sufficient for a tetrazo comp. VuioLET to blue BLack acid and developed (CrO,) 
dye. 

S. 288—‘‘Acid Alizarin Black SE.” Addition to 677,227. 


677,516—July 2, 1901. Adolf Israry and Richard Korus, Germany. (Elberfeld.) 
Red azo dye and process of making same. 
XyLIpIN, or other amin, amino azo compound, etc., 3 mols., coupled with 1 mol. guanidin 


compound described in 677,514 and 677,515, such as 5.5'5”-trioxy 7.7/7”-trisulfo 2-trinaphthyl 
GUANIDIN. ORANGE to RED direct dyes. 


677,517—July 2, 1901. Adolf Israrr, and Richard Korut, Germany. (Elberfeld.) 
Red azo dye and process of making same, 

Same as 677,516 but 2 mols., not 3, of diazo xyLIDIN, etc., are combined with 1 mol. of a 
dinaphthyl guanidin such as 5.5’-dioxy 7.7’-disulfo 2-dinaphthyl GUANIDIN. ORANGE to blue-RED 
direct dyes, very fast to acids and light. 


678,323—July 9, 1901. Moritz Utricu and Karl Hr1pEnricH, Germany. (Elberfeld.) 
Orange disazo dye and process of making same. 

3.3/Diamino DIPHENYL urea tetrazotized and coupled with 2 mols. 2-AMINO 5-NAPHTHOL 7- 
sulfo, or 1 mol. of this with 1 mol. of saricyLic or naphthionic acid or other aromatic carbo acid. 
ORANGE to RED direct or developed (coupled) dyes that can be diazotized on fiber, etc., and then 


are fast to washing. 
Near S. 297—‘“‘Benzo Fast Rose 2B.” Note 687,171. 


679,221—July 23, 1901. | O. Ernst, Germany. (Hoéchst.) 
Black polyazo dye and process of making same. 

4-PHENYLENE DIAMIN aZO I-NAPHTHYLAMIN 6- or 7-sulfo, coupled in alk. soln. with 2-AMINO 
8-NAPHTHOL 6-sulfo, azO 3-PHENYLENE DIAMIN, heated to 60° and pptd. by salt. Buacx direct 


dye. 
S. 436—“Columbia Black FB.” 


679,974—Aug. 6, 1901. August L. Lasxa, Germany. (Oehler.) 
Blue-red disazo dye and process of making same. 

BEnz1p1N, or other diamin, coupled with 1 mol. each of saricyLic acid, or other, and benzoyl 
2-AMINO 5-NAPHTHOL 7-Ssulfo. Blue-rEp direct dyes, fast to light and washing. 

Near S. 346—‘‘Oxamin Red.” 


* 
A. 
ke 

» 
; 


GROUP VI.—AZO 127 


680,283—Aug. 13, 1901. Karl ScurrmacuHer, Germany. (Héchst.) 
Black disazo dye and process of making same. 


2.6-Diamino PHENOL 4-sulfo, coupled with 1 mol. each of 2-NAPHTHOL and 2-NAPHTHOL 6-sulfo, 
or any mono, di or tri oxy or amino or sulfo deriv. of benzene, naphthalene, etc. Brown or 
BLACK fast acid or developed (CrO,) dyes. 

S. 289—‘“‘Acid Alizarin Black SN.” 


682,510—Sept. 10, 1901. Walter VoIcTLANDER-TETZNER, Germany. (Badische.) 
Blue disazo dye. 


Dianisipin, coupled with 1 mol. each of phenyl 2-amino 5-NAPHTHOL 7-sulfo and 1-AMINO 
8-NAPHTHOL 5- or 4-sulfo. Brug direct dye. 


683,119—Sept. 24, 1901. Oskar Kartwasser and Hugo Jarsscuin, Germany. (Berlin.) 
Bluwe monazo dye. 

2-Nitro 4-chlor PHENOL or isomer, reduced to amino compound with bisulfite then coupled 
with 1-AMINO 8-NAPHTHOL 2.4-disulfo. 

Note’ 683,120 and 684,065. 


683,120—Sept. 24, 1901. Oskar Kaurwasser and Hugo Jarsscuin, Germany. (Berlin.) 
Black disazo dye. 

I-NAPHTHYLAMIN, coupled with 1-AMINO 8-NAPHTHOL 4-sulfo, then combined with diazo 4- 
chlor 2-amino PHENOL 6-sulfo. Buiacx direct and developed (CrO,) dye, which when chromed is 
fast to soap and milling, and deeper. 

Near S. 220—‘‘Palatin Black A.”’ Note 683,119 and 684,065. 


683,190—Sept. 24, 1901. Richard TaccrseLtt, New York. (Schoellkopf.) 
Brown dye and process of making same. 

3-Amino tolyl oxamin sulfo acid A or B, coupled in alk. soln. with 2-am1no 8-NAPHTHOL 
6-sulfo “Gamma,” saponified, then tetrazotized and coupled with 2 mols. 3-PHENYLENE DIAMIN, or 
isomers, finally combined with two mols. diazo NAPHTHIONIC acid, or other. 

Near S. 488—‘‘Toluylene Brown R.” 


684,065—Oct. 8, roo1. Hugo Jarsscu1n and Oskar Katitwasser, Germany. (Berlin.) 
Blue azo dye and process of making same. 

4-Chlor 2-nitro PHENOL 6-sulfo, reduced to amino compound with bisulfite, then coupled with 
I-AMINO 8-NAPHTHOL 3.6-disulfo, in alk. soln. For first component the isomer obtained by sulfo- 
nating chlor amino phenol may be employed. BuuveE acid mordant (Cu) fast dye. 

Addition to 683,119. 


687,171—WNov. 19, 1901. Moritz Unricu and Karl Heipenricu, Germany. (Elberfeld.) 
Disazo dye and process of making same. 
4.4'-Diamino 3.3/-disulfo DIPHENYL urea, produced by action of PHOSGENE OM 4-NITRANILIN 
3-sulfo and reduction, or by direct action upon 4-PHENYLENE DIAMIN 3-sulfo, coupled with 2 mols. 
2-amino 8-NAPHTHOL'or its sulfo or alkyl derivs. Rep to red vioLet direct dyes, fast to light. 
S$. 297—‘‘Benzo Fast Rose 2BL.” 


688,478—Dec. 10, 1901. Oscar Muruuer, New York. (Schoellkopf.) 
Black dye and process of making same. 

Benzip1n, or other para diamin, tetrazotized and coupled in acetic acid soln. with 1-amMINo 
8-NAPHTHOL 3.6-disulfo, excess Na,CO, added, and diazo aniLin followed after two hours by 
3-TOLUYLENE DIAMIN, or other. Brack direct dyes. 


688,647—Dec. 10, 1901. Paul Junius, Germany. (Badische.) 
Brown-red azo dye. 
4-Chlor 2-amino PHENOL 6-sulfo, coupled with 2-NAPHTHOL. Brown, RED or blue BLacK acid 


and developed (CrO,) dyes. 
Near S. 131—‘‘Permanent Orange R.” 


128 DIGEST OF PATENTS 


690,294—Dec. 31, 1901. Paul Junius, Germany. (Badische.) 
Red carbon dye lake. 


2-NAPHTHYLAMIN sulfo (either the 8, 5, 6, or 7 mono acid), coupled with 2-NAPHTHOL. Pro- 
duction of Ba lakes is described and lakes of Ca, Al, Pb, Zn, etc., also claimed. Rep acid dye 
suitable for lakes. No claim as acid dyes. 

S. 175—‘‘Silk Poncean G.” 


692,675—Feb. 4, 1902. Paul Jutivs and Akim Txatscu, Germany. (Badische.) 
Diazo dye and process of making same. (Process not claimed.) 


2-NITRANILIN 4-Sulfo, diazotized and converted in Na,CO, soln. to diazo phenol then coupled 
in alk. soln. with 1-amino 8-NaPHTHOL 4-sulfo. VuioLet, BLACK (Cr), or BLUE (Cu), direct and 
developed dyes. 

Near S. 157—‘‘Diamond Black PV.” 


692,676—Feb. 4, 1902. Paul Junius and Fritz GintHeErR, Germany. (Badische.) 
Disazo wool-dye and process of making same. 


2.6-Diamino PHENOL 4-sulfo, :tetrazotized and coupled with 2 mols. 2-NAPHTHOL. VIOLET and 
blue siacx direct and developed (CrO,) dyes, which when chromed are fast to light, water, wash- 
ing, steaming, boiling water, carbonization, etc. 

S. 288—‘‘Acid Alizarin Black SE.’ Note 693,670. 


693,670—Feb. 18, 1902. Karl ScHIRMACHER, Germany. (Hochst.) 
Disazo wool dye and process of making same. 


2.4-Diamino PHENOL 6-sulfo, tetrazotized and coupled with 2 mols. 2-NAPHTHOL. BrRowNn 
and sLack direct and developed (CrO,) dyes. 
Near S. 288—‘‘Acid Alizarin Black SE.’’ Note 692,676. 


695,238—Mar. 11, 1902. ' Franz ScHoLtt, Germany. (Hoéchst.) 
Orange-red dye and process of making same. 


6-Nitro 2-amino PHENOL 4-sulfo*, coupled in alk. soln with 4’-sulfo phenyl PYRAZOLONE carbo 
acid. Other components claimed. YELLOW to RED acid mordant and acid dyes, faster as mordant 
dyes. 

*Note that graphic formula for sulfo acid in patent is 5-nitro 6-amino phenol 3-sulfo and is 
not the compound called for by the text. 


695,811—Mar. 18, 1902. Paul Jutius and Fritz Guntuer, Germany. (Badische.) 
Red azo dye. 


1-Methyl sulfo 2-NAPHTHYLAMIN (position of sulfo group not shown, probably para), 
coupled with 2-NAPHTHOL. Violet-RED acid dye suitable for lakes (fast to aq.). 

For mfr. or sulfo deriv., see Intermediates, same number. Patentee calls this comp. “‘b- 
amino sulfo a-naphthyl methane.” 


695,812—Mar. 18, 1902. Paul Jutius and Moritz JAHRMARKT, Germany. (Badische.) 
Chloranisidin. Chlor anisidin, m.p 83°, acetyl deriv. m.p. 103°, etc. 


Nitro 4-dichlor BENZENE dissolved in methyl alc., solid KOH added, and refluxed to form 
nitro chlor ANISOL, which is boiled in dil. acetic acid with iron filings, excess carbonate added and 
distilled. When coupled with 2-naphthol above gives orange rED lakes and developed dyes fast to 
rubbing, washing light, acids and alks. 

S. 97—‘“Chloranisidin Scarlet.’”? Patent claims intermediate only, but is classed as dye. 


697,765—Apr. 15, 1902. Ernst WINTER, Germany. (Hochst.) 
Red cotton-dye and process of making same. 


2-AMINO 5-NAPHTHOL 7-Sulfo, condensed with PHENYL mustard oil, or other, to form sym-5- 
oxy 7-sulfo naphthyl phenyl thio urEA, which is combined with diazo 4-amino ACETANILID, OF 
other, in alk. soln. Violet-rED direct dye, fast to acids. 

Near S. 279—‘‘Benzo Fast Scarlet.” \ 


700,565—May 20, 1902. Conrad Scurausrk and Hans T. Bucuerrer, Germany. (Badische.) 
Azo dye and process of making same. 


1.8-NAPHTHALENE DIAMIN 4-Sulfo or disulfo (1.8.3.6), combined with 1-2 mols. of diazo 
4-NITRANILIN, or other, and condensed with AacETONE, which may be added before or after the 
diazo body. Rep to sive direct and acid dyes, fast to acid, alks., and carbonates. 


GROUP VI.—AZO 129 


703,105—June 24, 1902. Arthur WEINBERG, Germany. (Cassella.) 
Blue wool-dye and process of making same. 
2-Chlor 4-NITRANILIN, coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo, reduced in alk. soln. 


with Na,S and pptd. product alkylated in alc. soln., containing sod. acetate by heating at 90° 
with ETHYL bromid, or other. Buus acid dye, level and fast. 


704,825—July 15, 1902. Wilhelm HeErzperc and Otto Siesrert, Germany. (Berlin.) 


Red azo dye. 


4-Nitro 6-amino SALICYLIC acid, coupled in alk. soln. with 3-ToLUYLENE DIAMIN 4-tolyl sulfon- 
amid. Yellow-rEp acid and acid mordant dyes, which when chromed are fast to soap, milling, 


light, SO,. 
S. o92—Metachrome Bordeaux R. Note 561,985 for method of dyeing; also 704,826. 


704,826—July 15, 1902. Wilhelm HeErzsperc and Otto S1EBERT, Germany. (Berlin.) 
Red azo dye. 

Picramic acid, coupled in alk. soln., with 3-ToLUYLENE DIAMIN 4’-tolyl sulfonamid made as in 
704,825. Other components\claimed. Rep acid and acid mordant dyes, which when chromed are 


fast to soap, milling, light, and SO,. 
S. o92—‘‘Metachrome Bordeaux R.” 


709,186—Sept. 16, 1902. Arthur WEINBERG and Felix KiinceMann, Germany. (Cassella.) 
Blue dye and process of making same. 


I-NAPHTHYLAMIN 6- or 7-sulfo “‘Cleves’? or amino derivs. in para position to amino group, 
coupled in HCl soln. to a second mol. of same, again coupled in acetic soln. with a third mol. 
of same, and finally diazotized and coupled with 2-aMINO 5-NAPHTHOL 7-Ssulfo in alk. soln. Buuz 
direct dye, fast to light. ‘ 


710,059—Sept. 30, 1902. Paul Jutius, Germany. (Badische.) 
Brown-violet azo dye. 

1-Chlor 2-NAPHTHYLAMIN 5-sulfo or 2-naphthylamin 1.5-disulfo, coupled with 2-NAPHTHOL, 
warmed to 35-80°. Vari-colored acid and developed (CrO,, Cu) dyes. 

Note 737,907 and 770,177. 


713,507—WNov. 11, 1902. 
Conrad ScurausE and Walter VoIGTLAENDER-TETZNER, Germany. (Badische.) 


Red disazo dye and process of making same. (Product only claimed.) 

Benzipin, coupled with 1 mol. each of saticyLic acid and 1-NaAPuTHOL 3-sulfo or beta sub- 
stituted compounds of same, see examples and table. Rep acid and developed (CrO,) dye, fast 
to fulling, and faster to light than alfa substitute. 


714,882—Dec. 2, 1902. Otto Ernst, Germany. (Hochst.) 
Monoazo dye and process of making same. 
4-NITRANILIN 2-sulfo, coupled with 2-narpHtTHoL. Rep lakes, fast to water, acid, lime, and 


especially to light. 
S. 3132—“Lake Red P.” Note 714,883. 


714,883—Dec. 2. 1902. Otto Ernst, Germany. (Hoéchst.) 
Orange-yelluw azo dye and process of making same. 

2-NITRANILIN 4-Sulfo, coupled with 2-NAPHTHOL. Orange YELLOW dye yellower than isomer 
from 4-nitranilin 2-sulfo, suitable for lakes; fast to water, acid, lime, and especially light. 

S. 148—‘Fast Orange O.”’ Addition to 714,882. 


716,242—Dec. 16, 1902. Paul Junius, Germany. (Badische.) 
Disazo dye and process of making same. 

4-Chlor 6-amino saticytic acid, coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo, again diazotized 
and coupled with 2-naPHTHOL. Violet-pLack acid and developed (CrO,) dye, level and fast to 
fulling, milling, potting and ironing. 


130 DIGEST OF PATENTS 


717,550—Jan. 6, 1903. Jens Dxpicuen, Germany. (Berlin.) 
Process of making black polyazo dyes. 

Benziwin, coupled with 1-aAMINO 8-NAPHTHOL 3.6-disulfo in acid soln., then in alk. soln., 
with 3-PHENYLENE DIAMIN, or homolog, and finally with diazo aNniL1N, or homolog, in alk. soln. 
The final component is attached to the meta diamin, not to naphthol sulfo as in 688,478. Green 


BLACK direct dye. 
S. 462—‘“‘Erie Direct Black GX.’’ 


716,289—Dec. 16, 1902. 
Conrad ScurausBe, Erhart ScHLEICHER, and Theodor Bucngrer, Germany. (Badische.) 


AZO dye. 


1.8-NAPHTHALENE DIAMIN 5-Sulfo or other, heated at 90-95° in sulfite soln. (40°), to form 
a sulfurus acid ester that is diazotized and coupled with 2-NnaApHTHOL. The above may be com- 
bined with diazo anilin to a disazo dye. Note test for sulfurus acid present and table of com- 
ponents. Vart-colored acid dyes. 


718,028—Jan. 6, 1903. 
Conrad ScurauBeE and Walter VoIGTLANDER-TETZNER, Germany. (Badische.) 
Mixed disazo dye and process of making same. 


I.5-NAPHTHALENE DIAMIN, coupled with 1 mol. each of sanicytic acid and 2-NAPHTHOL 
3.6-disulfo or other coupling agent. See list of 30 components claimed. Vari-colored acid 
mordant or developed (CrO,) dyes, fast to fulling. 


718,032—Jan. 6, 1903. Walter VoIGTLANDER-TETZNER, Germany. (Badische.) 
Azo dye and process of making same. 


3-TOLUYLENE DIAMIN azo SALICYLIc acid, derived from meta nitro comp. by reduction or 
from the acetylated diamino comp. by saponification, coupled in alk. soln. with 1-NAPHTHOL 
4-sulfo, or other. Rep to Brown direct and developed (CrO,) dye, fast to light and fulling. 


718,181—Jan. 13, 1903. Arthur WEINBERG, Germany. (Cassella.) 
Blue wool-dye and process of making same. 


as-Acetyl ethyl 4-PHENYLENE DIAMIN, coupled with cHromoTropic acid, or other, then saponi- 
fied by boiling in five per cent NaOH. Buve acid dye, fast to light. 

Near S. 67—‘“‘Chromotrop 6B.’ The amin may be termed 4-amino ethyl acetanilid, or 
4-amino acetyl ethyl anilin. 


718,356—Jan. 13, 1903. Paul Junius, Germany. (Badische.) 
Red azo dye. 


2-NAPHTHYLAMIN 1.5-disulfo, Na salt, dissolved in twenty per cent NH,, coupled with 2- 


NAPHTHOL. Rep dye for lakes. 
Near S. 173—‘‘Lithol Red R.” 


718,389—Jan. 13, 1903. 
Conrad ScurausBE and Walter VoIGTLAENDER-TETZNER, Germany. (Badische.) 
Red azo dye. 
BeEnzIpIN, or other, coupled with 1 mol. each of 2-NAPHTHOL 6.8-disulfo and 4-crEsoL. RED 
direct dye, fast to fulling. 


719,048—Jan. 27, 1903. Friedrich RuNKEL, Germany. (Elberfeld.) 
Yellow azo dye and process of making same. 
SuLFANILIC acid, coupled with 2-methyl 1npoLtg. See table of components claimed. YELLow, 


ORANGE, to BROWN acid dyes. 
Note 719,049. 


719,049—Jan. 27, 1903. Friedrich RunKeL, Germany. (Elberfeld.) 
Yellow azo dye and process of making same. 

2-Methyl 1npoLE, or other, sulfonated in fuming sulfuric, twenty per cent SO,, below 60°, 
then product combined with diazotized 2-toLuipin. Other components claimed. YELLow to 
ORANGE acid dye, fast to light. 

Addition to 719,048. 


z 
i 
‘ae 
j 


GROUP VI.—AZO 131 


722,715—Mar. 17, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Wool-dye and process of making same. 

2-Amino PHENOL 4-sulfo, coupled with 1.5-dioxy NAPHTHALENE. Violet-rED and sBLacK acid 
and developed (CrO,) dyes, fast to potting, milling, washing and light. 

Note 722,716, 725,848, 726,695, and 727,965 to 67. 


722,716—Mar. 17, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Wool-dye and process of making same. 

6-Amino 2-crEsoL 4-sulfo, or the ortho amino sulfo derivs. of either ortho, meta, or para 
cresol, coupled with 1.5-dioxy NAPHTHALENE. Violet RED and BLACK (CrO,) acid and developed 
dyes, fast to potting, milling, washing, and light. 

Addition to 722,715. 


722,860—Mar. 17, 1903. Ivan Levinstgin and Carl Menscuinc, England. (Levinstein.) 
Blue polyazo dye and process of making same. 


Benzyl 1-NAPHTHYLAMIN 8-sulfo, coupled with diazotized ANILIN azo I-NAPHTHYLAMIN 6- or 
7-sulfo. Buus acid dye, shades bluer than from unbenzylated component. 


724,078—Mar. 31, 1903. Albert BERTSCHMANN, Switzerland. (Basle.) 
Azo dye and process of making same. 


ANILIN, benzidin, etc., coupled with 3’-amino benzoyl 2-AMINO 5-NAPHTHOL 7-Sulfo in alk. 
soln. See list of other components claimed. ORANGE to RED acid and developed (coupled) dyes, 
fast to washing, and can be diazotized on fiber. 


724,743—Apr. 7, 1903. Carl Scu1rRMACHER, Germany. (Hoéchst.) 
Red ‘azo dye and process of making same. 


4-NITRANILIN 2-sulfo, coupled with 2-NaPHTHOL. Rep lakes. 
Near S. 56—‘‘Paranitranilin Red.” 


724,893—Apr. 7, 1903. August IL. Lasxa, Germany. (Oehler.) 
Violet azo dye and method of making same. 

BeENZIDIN, or other, coupled with 2 mols. of the glycin deriv. of 2-AMINO 5-NAPHTHOL 7-Sulfo, 
or other, in alk. soln., heated to 80°. VuoLEet to BLUE direct dye. 

S. 326—“‘Oxamin Violet.” Note 724,894 and 728,477; also 521,096, of which this is the 
glycin deriv. 


724,894—Apr. 7, 1903. August L. Lasxa, Germany. (Oehler.) 
Red to violet dyestuff and method of making same. 

Benzipin, or other, coupled with 1 mol. each of saLicynic acid and glycin of 2-AMINO 5- 
NAPHTHOL 7-sulfo. Other components claimed. Rep to vioLer direct dyes, fast to light and acids, 
and suitable for lakes. 

Near S. 346—‘‘Oxamin Red.”’ Addition to 724,893. 


725,848—Apr. 21, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Black azo dye. 


6-Nitro 2-amino PHENOL 4-sulfo, coupled with 1.5-dioxy NAPHTHALENE. Blue-vIoLET to BLACK 
acid and developed (CrO,) dyes, fast to potting, milling, washing and light. 
Addition to 722,715. 


726,695—Apr. 28, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Black azo dye. 

4-Chlor 2-amino PHENoL 6-sulfo, or other, coupled with 1.5-dioxy NAPHTHALENE. VIOLET to 
BLACK acid and developed (CrO,) dyes, fast to potting, milling, washing and light. 

Addition to 722,715. 


727,962—May 12, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Azo dye. 

2-Amino PHENOL 4-sulfo, coupled in alk. soln. with 2.6-dioxy NAPHTHALENE. Other compo- 
nents claimed. Rep to sLuE and sBLack acid and developed (CrO,) dyes which when chromed 
are fast to potting, milling, washing and light. 

Near S. 157—‘‘Diamond Black.” Note 729,601. 


132 DIGEST OF PATENTS 


727,963—May 12, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Azo dye. 


Amino PHENOL sulfo, or derivs., coupled with 1-AMINO 7-NAPHTHOL. VIOLET or BLACK acid 
and developed (CrO,) dye, fast to potting, washing, milling, and light. 
Addition to 722,715. 


727,964—May 12, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Monoazo dye. 


6-Nitro 2-amino PHENOL 4-sulfo, coupled with 1-AMINO 7-NAPHTHOL. BLUE or BLACK acid 
and developed (CrO,) dyes, fast to potting, milling, washing and light. 
Addition to 722,715. 


727,965—May 12, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Azo dye. 

2-Amino PHENOL 4-sulfo, or derivs., coupled with 1.5-dioxy NAPHTHALENE 3-sulfo. Violet- 
RED to blue-vioLET to BLACK acid and developed (CrO,) dyes, fast to potting, milling, washing 
and light. 

Addition to 722,715. 


%727,966—May 12, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Monoazo dye. 

6-Nitro 2z-amino PHENOL 4-sulfo and substituted products, coupled with 1-AMINO 7-NAPHTHOL 
4-sulfo. Violet-RED, BLUE or BLACK acid and developed (CrO,) dyes, which when chromed are 
fast to potting, milling and washing, and very fast to light. 

Addition to 722,715. 


727,967—May 12, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Black azo dye. 

2-Amino PHENOL 4-sulfo, or derivs., coupled with 2-AMINO 6-NAPHTHOL. Red-vIOLET, BLUE, 
and BLacK acid and developed (CrO,) dyes which when chromed are fast to potting, washing, 
milling, and light. 

Near S. 157—‘‘Diamond Black.’’ 


728,021—May 12, 1903. Albrecht Scumipt, Germany. (Hochst.) 
Black azo dye and process of making same. 


NAPHTHIONIC acid, or other, coupled in weak acid or alk. soln. with 1.8-NAPHTHALENE DIA- 
MIN 4-Sulfo, and then heated with mineral acid, which apparently converts thé diamin into an 
amino naphthol sulfo comp. Heating with acid may precede coupling. A diazo comp. can be 
coupled with the product to form disazo dye. VuioLEeT and BLACK acid dyes. 


728,388—May 19, 1903. Emile A. Fournraux, New York. (Metz.) 
Azo dye and process of making same. 

Diazo 4-NITRANILIN, or other, and diazo suLFANILIC acid, or other, in equimolecular amounts 
coupled with 2-NAPHTHOL to form a gelatinous paste suitable for lake formation. Patentee 
claims the nitro diazo component “displaces” the sulfo. The proportion of naphthol coupling 
agent is not definite. Violet-rEp lakes, fast to light. 

Near S. 56—‘‘Paranitranilin Red.’? Note 728,455. 


728,455—May 19, 1903. Emil A. Fourngaux, New York. (Metz.) 
Azo dye and process of making same. : 


4-NITRANILIN, coupled with 2-NAPHTHOL, 0.75 mol., and 2-NAPHTHOL 7-Sulfo, 0.25 mol. Prod- 
uct is very finely divided or gelatinous and suitable for lakes pptn. Other components claimed. 
Patentee claims use of second phenolic coupling agent in “such proportions” as to secure finely 
divided condition of dye. Patent differs from others that use five per cent or less of sulfonated 
2-naphthol for toning purposes. Violet-rEp lakes, fast to light. 

Near S. 56—‘‘Paranitranilin Red.’? Note 728,388. 


728,477—May 19, 1903. August L. Lasxa, Germany. (Oehler.) 
Blue disazo dye. (Process also claimed.) 
Dianisip1n, coupled with 1 mol. each of the glycin of 1-AMINO 8-NAPHTHOL 3.6-disulfo and 
2-NAPHTHOL, or derivs. Other components claimed. Buiue direct dyes, fast to light and acids. 
Addition to 724,893. 


SO ngia'y 


: 
t 
§ 
a 
‘ 
c 


GROUP VI.—AZO 133 


729,601—June 2, 1903. Myrtil Kaun, Germany. (Elberfeld.) 
Azo dye and process of making same. (Process not claimed.) 


2-Amino PHENOL 4-Sulfo, coupled in alk. soln. with 1-AMINO 5-NAPHTHOL. Other components 
claimed. Vioier and siack acid and developed (CrO,) which when chromed are fast to potting, 
milling, washing, and light. 

Near S. 157—‘‘Diamond Black.” Addition to 727,962. 


731,460—June 23, 1903. Adolf Israzyn and Oscar DresseL, Germany. (Elberfeld.) 
Bluish-violet azo dye. 


Acetyl 2-chlor 4-PHENYLENE DIAMIN, derived from nitro comp. (2-chlor 4-nitranilin), coupled 
with 1.8-dioxy NAPHTHALENE 3.6-disulfo or ‘“‘Chromotropic acid.’”’ Blue-viotetT acid dye, fast 
to light. 


733,280—July 7, 1903. Karl ScurrmMacHer, Germany. (Héchst.) 
Red azo dye and process of making same. 


4-Chlor 3-ToLuip1n 6-sulfo (NH,== 1), formed by reduction of the nitro compound, coupled 
with 2-naPHTHOL. Rep lakes, Ba salt fast and of good color. 
S. 153—“Lake Red C.” Note 983,486. 


737,445—Aug. 25, 1903. Eduard Muncnu, Germany. (Badische.) 
Reddish-brown 2zo dye. : 


ANTHRANILIC acid coupled with 4-crEsotr. Red-srown acid mordant dye. 


737,967—Sept. 1, 1903. Frederich Scumipt, Germany. (Héchst.) 
Violet-red azo dye and process of making same. 
2-NAPHTHYLAMIN 1.5.7-trisulfo, diazotized, soln. exactly neut., then with excess alk. carb., 


the ortho sulfo group is changed to OH and the resulting diazo oxid is coupled with 2-NAPHTHOL. 
Note 770,177 and 710,050. 


739,069—Sept. 15, 1903. Otto Ernst and Franz Scuoit, Germany. (Hdéchst.) 
Red mordant azo dye. (Process also claimed.) 
3-Amino 4-crESoL 5-sulfo, or the (3.2.5) or (3.4.6) comps., coupled with phenyl pyRazoLone, 


or derivs. Orange-yELLow and rrp acid and mordant (Cr) dyes, chromium lake as fast to light 
as alizarin dyes. 


739,118—Sept. 15, 1903. Otto Soust, Germany. (Hochst.) 
Monoazo dye and process of making same. 

Acetyl 2.5-diamino HYDROQUINONE, dialkyl-ether, coupled with 1.8-dioxy NAPHTHALENE 3.6- 
disulfo, then hydrolyzed, or the original nitro-amino hydroquinone may be first coupled, then 
reduced. Green-BLUE acid dye, easily discharged, fast to alkali, water, washing, and suitable 
for printing. 


740,767—Oct. 6, 1903. August L. Lasxa, Germany. (Ocehler.) 
Mordant disazo dye and process of making: same. 

4-NITRANILIN 2-sulfo, coupled in alk. soln. with 2-aAMINO 5-NAPHTHOL 7-sulfo, then combined 
in strong alk. soln. with diazo picramic acid. Other components claimed. Blue-Biack acid mor- 
dant (Cr) dye, fast to light, acids, alks., milling. 


740,768—Oct. 6, 1903. August L. Laska, Germany. (Oehler.) 
Black mordant dye and process of making same. 
2-NAPHTHYLAMIN 3.6-disulfo, coupled in acid soln. with 2-AMINO 5-NAPHTHOL 7-Sulfo, then 


combined in alk. soln. with diazo prcramic acid or other nitroamino phenol. Buxuacxk acid mor- 
dant (Cr) dye, fast to light, acids, alks., and milling. 


741,552—Oct. 13, 1903. Franz Scuoit, Germany. (Héchst.) 
Process of making azo dyes. 
6-Nitro 2-amino PHENOL 4-sulfo, or other ortho amino phenol, coupled with 1.8-azimino 


NAPHTHALENE 4-sulfo. in large excess alkali. Buur acid dyes. 
Near S. 159—‘‘Acid Alizarin Black R.” 


134 DIGEST OF PATENTS 


741,936—Oct. 20, 1903. Erhart ScuigicHer and August Dorrer, Germany. (Badische.) 
Dizazo coloring-matter. 


SULFANILIC acid, naphthionic acid, or 2-naphthylamin 8-sulfo, 2-mols., coupled with one mol. 
1.5-dioxy NAPHTHALENE, the first mol. in acetic soln. and second in alk. soln., or both in alk. soln. 
below 0°. Rep to vIOLET to BLACK acid and developed (CrO,) dyes. 

Near S. 212—‘‘Fast Brown G.” 


743,071—Nov. 3, 1903. Richard Grey and Otto Sirsert, Germany. (Berlin.) 
Monoazo dye and process of making same. 

4-TOLUIDIN 2-sulfo, or 2 sulfo 4-chlor or 4-nitranilin, coupled in alk. soln. with 2-oxy NAPH- 
tHorIc acid. Red dye, suitable for lakes, fast to aq., oil, light. 

Near S. 152—‘‘Lithol Rubin B.” Note 741,029. 


748,076—Dec. 29, 1903. Adolf Isragy and Richard Kotur, Germany. (Elberfeld.) 
Trisazo dye. 

Acetyl 4-PHENYLENE DIAMIN, coupled in alk. soln. with 2-am1no 8-NAPHTHOL 6-sulfo, saponi- 
fied, tetrazotized and coupled in acetic soln. with acetyl 4-amino 3-phenylene diamin, then in alk. 
soln. with 3-TOLUYLENE DIAMIN. Other components claimed. Buacx direct dye. 

Note Ser. 150,763 (4-2-1903), above pat. is Ser. 150,754. 


748,195—Jan. 12, 1904. Meinhard Horrman, Germany. (Cassella, N. Y.) 
Dark-blue wool-dye and process of making same. 

Acetyl 2.4-diamino phenol 6-sulfo, coupled with 2-NAPHTHOL, or other. BLuE to BLACK acid 
mordant dye, fast. 


749,195—Jan. 12, 1904. Meinhard Horrman, Germany. (Cassella, N. Y.) 
Dark-blue wool-dye and process of making same. Acct. 2.4-diamino phenol 6-sulfo. 


Acetyl 4-amino PHENOL added to conc. H,SO,, heated to 95°, cooled, and mixed acids (1:1) 
added below 5°, diluted and reduced with Zn dust below 30°. 


752,562—Feb. 16, 1904. Paul Junius. Germany. (Badische.) 
Red azo dye. 
4-Chlor ANILIN 5- or 6-sulfo, coupled with 2-NAPHTHOL. Product forms rED Pb, Ba, Ca or 


Al lakes, insol. in aq. or alc. 
Near S. 153—‘‘Lake Red C. paste.” 


754,315—Mar. 8, 1904. Paul Jutius and Ernst Fusseneccrer, Germany. (Badische.) 
Azo dye and process of making same. 


Methyl 4-PHENYLENE DIAMIN HCl, diazotized with double quantity of nitrate to form a 4- 
diazo methyl phenyl nNrtTROSAMIN, which is coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo. ‘The 
nitrous dye gives red color in acetic bath, but in HCI the nitroso group is split off and dye is 
blue. Rep or BLUE acid dye. 


754,856—Mar. 15, 1904. August Dorrer, Germany. (Badische.) 
Red-violet azo dye. 

NapPuTHIONIC acid, 2-naphthylamin-8-sulfo, sulfanilic or metanilic acid, coupled with 1.8- 
NAPHTHALENE DIAMIN. When product in dil. HCI below 5° is treated with nitrite, an amino 
comp. forms and when this is reduced by Zn and NH, the original amino sulfo comp. is re- 
stored and 1.8.4-triamino naphthalene forms. Test for triamino component after reduction is 
given. Violet-srown acid and developed (CrO,) dyes. 


757,109—Apr. 12, 1904. Gillis GuLLBRANssON, Germany. (Hoéchst.) 
Blue-red lake and process of making same. 


ANTHRANILIC acid, coupled with 2-NAPHTHOL 3.6-disulfo “R.” Three methods for pptn. of 
dye lake given. Violet-rEp lakes, faster to light and almost as brilliant as eosin. 
S. 202—‘‘Acid Alizarin Red B.” 


759,284—May 10, 1904. Karl JAGERSPACHER and Thilo Kroser, Switzerland. (Basle.) 
Blue-azo dye and process of making same. 


Acetyl 2.5-diamino 4-chlor PHENOL, methyl ether, or other, coupled in alk. soln. with 1.8- 
dioxy NAPHTHALENE 3.6-disulfo, or other peri-dioxy naphthalene sulfo acids. 
Note 739,118 (Hochst) and 749,195 (Cassella). 


GROUP VI.—AZO Peet Si 


759,613—May 10, 1904. Karl Jepiicxa, Switzerland. (Basle.) 
Violet tetrazo dye and process of making same. 

BENZIDIN or other, coupled in acid or alk. soln. with 2 mols. 2-AMINO 5-NAPHTHOL 1.7- 
disulfo or one mol. of this and one of 1-NapHTHOL 4-sulfo or other. VIOLET, BLUE and BLACK 
direct and developed (coupled) dyes, which when diazotized on fiber are fast to washing. 

Near S. 526—‘‘Oxamin Violet.” 


759,716—May 10, 1904. Paul Juxius and Siegfried HarcKEL, Germany. (Badische.) 
Red azo dye. i 

3-Chlor 4-ToLuIDIN 6-sulfo (NH, = 1) coupled with 2-napHtHoL. RED lakes, those with Ca. 
Ba, Al and Pb, being fast aq., acid, alk., light. 

Near S. 153—‘‘Lake Red”. Note 765,079, 765,080, and 733,280. 


761,123—May 31, 1904. Hugo Wirrer, Germany. (Elberfeld.) 
Red azo dye. 


1-AminoO ANTHRAQUINONE coupled with 2-NAPHTHOL 6.8-disulfo. Other component claimed. 
Red acid dye, suitable for lakes with Ca, Ba, Sr, Mg, Al, etc., fast to light. 


763,761—June 28, 1904. Karl JEpnicua and Arnold Scurpier, Switzerland. (Basle.) 
Orange tetrazo dye and process of making same. 

3.3'-AZOXY di-ANILIN derived from 3-nitranilin by alk. reduction, as in 380,927, or other, 
coupled with 2 mols. 2-AMINO 5-NAPHTHOL 7-sulfo or of 2-AMINO 5-NAPHTHOL, 1.7-disulfo or sali- 
cylic acid, etc., see list. ORANGE to RED direct dyes. 


765,079—July 12, 1904. Paul Junius and Carl Winter, Germany. (Badische.) 
Red azo color. 
3-Chlor 4-ToLurpiIn (NH, = 1) coupled in alk. soln. with 2-NAPHTHOL 3.6-disulfo. Rep lakes, 


fast to light. 
Addition to 759,716. 


765,080—July 12, 1904. Paul Junius and Franz OstHELpER, Gemany. (Badische.) 
Yellow-red azo color. 

3-Chlor 4-ToLuipIN, coupled with 2-NapHTHOL in alk. soln. containing Turkey Red oil, 
oleic acid or soap, etc. RED, YELLOW and oRANGE, developed dyes, suitable for printing or as 


lakes. 
Near S. 153—‘‘Lake Red C.”? Addition to 759,716. 


765,581—July 109, 1904. Paul Junius and Siegfried HarcKEL, Germany. (Badische.) 
Azo dye and process of making same. 

2.4-Dichlor 1-NAPHTHYLAMIN 7-sulfo diazotized, soln. made strongly alk. with carb. and 
heated at 60° until it is clear and couples violet with resorcin. Probably an OH group replaces 
one Cl to form hydroxy chlor diazo naphthalene sulfo or anhydride may result from loss of 
water, and resulting diazo 2-oxy 4-chlor 1-naphthyamin 7-sulfo is coupled with 2-NAPHTHOL, 
VIOLET and BLack acid and developed (CrO,) dyes. 


767,070—Aug. 9, 1904. August L. Lasxka, Germany. (Oehler.) 
Brown mordant dye. (Process also claimed.) 

2-AMINO 5-NAPHTHOL 7-sulfo or other, coupled with 3-oxy DIPHENYLAMIN.. See table of other 
components claimed. ORANGE to vIOLET acid dyes, fast to light, milling and potting. 

Addition to 767,069. 


767,069—Aug. 9, 1904. August L. Lasxa, Germany. (Oehler.) 
Dark-brown wool-dye. (Process also claimed.) 

Naputuionic acid, or other, coupled in alk. soln. with 3-oxy DIPHENYLAMIN. Brown, acid 
and developed (CrO,) dyes. Note addition pat. 767,070. 


\ 


770,177—Sept. 13, 1904. 
Paul Junius, Hans RernpeL, and Fritz Gunruer, Germany. (Badische.) 


Azo dye and process of making same. 
I-NAPHTHALAMIN 2.4-disulfo or other ortho amino sulfo comp. diazotized, soln. neut. then 
hypochlorite or Cl vapor and excess Na,CO, added and coupled with 2-NaPpHTHOL. ‘The ortho 


136 DIGEST OF PATENTS 


sulfo group is replaced by OH and resulting diazo oxid couples to form ortho-oxy azo comp. 
VIOLET, RED to BLACK, direct and developed (CrO,) dyes. 
S. 181—“Palatin Chrome Black B.” Note 737,967 and 710,059. 


770,430—Sept. 20, 1904. Wilhelm Herzperc and Otto Siesert, Germany. (Berlin.) 
Red lake. 

4-ANISIDIN 3-Sulfo or other, coupled with 2-napHTHOL and lake pptd. by BaCl, or ZnCl, and 
Al (OH),. Sr, Ca, Mg, and Al, lakes may be formed. Rep lakes, fast to aq., alc., oils and 
fats, etc. 

Note 765,079 and 750,716. 


778,476—Dec. 27, 1904. Karl Exper, Germany. (Kalle.) 
Beta-naphthol azo dye and process of making same. 

I-AMINO 2-NAPHTHOL 3.6-disulfo diazotized in strong acetic-sodium acetate soln., coupled 
in conc. alk. carb. soln. at 30—40° with 2-NAPHTHOL. Other components claimed. REp to VIOLET 


to BLACK, acid and developed (CrO,) dyes. 
Near S. 181—‘‘Palatin Chrome Black 6B.” 


778,610—Dec. 27, 1904. Karl ScuHriRMACHER, Germany. (Hochst.) 
Black disazo dye and process of making same. 

PHENYLENE DIAMIN disulfo, diazotized with excess nitrite to prevent formation of Vesuvin 
instead of tetrazo phenyl sulfo compound, coupled with 2 mols. 2-NAPHTHOL. RED, BROWN and 
BLACK, direct and developed (CrO,) dyes. 


786,767—Apr. 4, 1905. Paul Juntius and Ernst FussenreccER, Germany. (Badische.) 


Blue-red azo dye. 
3.4.6-Trichlor ANILIN diazotized with nitrosyl sulfuric acid, coupled with 2-NAPHTHOL 3.6- 
disulfo ‘‘R.”’” Rep lakes (Ba, Al), fast to light. 


787,046—Apr. 11, 1905. August L. Lasxka, Germany. (Oehler.) 
Claret-red mordant dye and process of making same. 

2-Nitro 6-amino PHENOL 4-sulfo coupled with 3-crEsoTinic acid or other. Rep acid mordant 
(Cr) dyes fast to light, milling and steaming. 


787,767—Apr. 18, 1905. Paul Jutius and Ernst Fusseneccrer, Germany. (Badische.) 


Orange-red azo dye. 

3-4-Dichlor nitro BENZENE sulfonated, then reduced to form 3.4-dichlor aniLiIn 5-sulfo, or 
3.4-dichlor anilin is sulfonated to form 3.4.6 comp., diazotized and coupled with 2-NAPHTHOL. 
ORANGE to RED acid dyes, fast to light and suitable for lakes (Ba, Al). 

Note 787,768 and 789,096. 


787,768—Apr. 18, 1905. Paul Junius and Ernst Fussengeccrer, Germany. (Badische.) 


Blue red azo dye. 

3.4-Dichlor ANILIN coupled with 2-NAPHTHOL 3.6-disulfo ‘“‘R.’’ Rep acid dyes fast to light, 
suitable for lakes (Cr. Al). 

Addition to 787,767. 


789,096—May 2, 1905. Paul Jutius and Ernst FusseNEGCER, Germany. (Badische.) 


Azo dye. 

4-Chlor aninin coupled with 2-NAPHTHOL 3.6-disulfo “R.”’ Rep dye, suitable for lakes (Ba), 
fast to aq., light and of good covering power. 

Addition to 787,767. 


790,363—May 23, 1905. John Hacensacu, Switzerland. (Geigy.) 


Nitroazo dye and process of making same. 

I-AMINO 2-NAPHTHOL 4-sulfo diazotized, separated as dry powd., nitrated in H,SO, soln. then 
coupled with 2-NAPHTHOL. Brown to BLACK, acid and developed (CrO,) dyes which when 
chromed are fast to light, milling and potting. 

S. 184—‘‘Eriochrome Black. Note 790,364. 


GROUP VI.—AZO 137 


790,364—May 23, 1905. John Hacensacu, Switzerland. (Geigy.) 
Azo dye and process of making same. 

I-AMINO 2-NAPHTHOL 4-sulfo coupled with 2-NaPpHtTHOL, and as dry powd. sulfonated. Rep 
to BLACK acid and developed (CrO,, Cu) dyes very soluble in aq. 

Near S. 181—‘Palatin Chrome Black 6 B.” Addition to 790,363. 


791,524—June 6, 1905. Hugo Wirrer, New York. (Elberfeld.) 
Yellow dye. 

BENZIDIN 2.2’-disulfo, or other, coupled with 2 mols. phenyl methyl pyRrazoLoNE YELLOW. 
Acid dye, fast to milling. 

Note 791,525 and 26. 


791,525—June 6, 1905. Hugo Wirter, New York. (Elberfeld.) 
Yellow dye. 

BENZIDIN 2.2’-disulfo or other, coupled in acetic soln. with 2-methyl rnpoLz, then with phenyl 
methyl PyRAZOLONE. YELLOW acid dyes, fast to milling, will not bleed. 

Addition to 791,524. 


791,526—June 6, 1905. Hugo Wirrer, New York. (Elberfeld.) 
Yellow tetrazo dye. 
BENZIDIN 2.2’-disulfo or other, coupled with 2 mols. 2-methyl 1npoLx. YELLow acid dyes, 


fast to milling. 
Addition to 791,524. 


792,082—June 13, 1905. Martin Hrrzperc, New York. (Elberfeld.) 
Blue-black azo dye. 


3-Nitro acetyl 4-PHENYLENE DIAMIN coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo., or 
other, then saponified by boiling in acid or alk. REp, VIOLET or BLUE-BLACK acid dyes. 
Near S. 57—‘“‘Chromotrop. 2B.” and S$. 61—‘Victoria Violet.” Note 792,033 and 34, 


7975731-32. 


792,033—June 13, 1905. Martin Herzprerc, New York. (Elberfeld.) 


Black azo dye. 

3-Nitro acetyl 4-PHENYLENE DIAMIN, coupled in acetic soln. with 1-AMINO 8-NAPIITLOL 3.6- 
disulfo. Briacx acid mordant dye. 

Addition to 792,032. 
792,084—June 13, 1905. Martin Herzperc, New York. (Elberfeld.) 
Azo dye. 

3-Nitro acetyl 4-PHENLENE DIAMIN, coupled in alk. soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo 
“H.” or other. Buiack or violet-rED (acetyl comp.) acid dyes. 


Addition to 792,033. Components are same as those in preceding patent but coupling 
medium is alk. instead of acid. 


792,421—June 13, 1905. Paul Junius, and Ernst FusseNEGcER, Germany. (Badische.) 
Azo dye adapted to form lakes. 


5-Nitro 2.4-xYLIDIN, or other, with nitro and amino groups in ortho and para positions to a 
methyl group coupled with 2-NAPHTHOL 3.6-disulfo “R.’”? Rep dye suitable for lakes (Ba) fast 


to aq. 
794,568—July 11, 1905. Alfred THauss, New York. (Elberfeld.) 


New azo dye. 
2-TOLUIDIN, or other, coupled in alk. soln. with 3’-amino phenyl 5-oxy 7-sulfo 1.2-NAPHTHI- 
AZOLE. Rep direct dyes that be diazotized on fiber, then are fast to washing. 


792,600—June 20, 1905. Karl KREKELER, and August BLanx, New York. (Elberfeld.) 


Reddish azo dye. ' 
2-TOLUIDIN, or other, coupled in alk. soln. with 3’-amino phenyl 5-oxy 7-sulfo 1.2-NAPHTIMID- 
AZOLE or other. Rep to violet-siug direct dyes that can be diazotized on fiber to obtain a red 


fast to washing. 


138 DIGEST OF PATENTS 


794,568—July 11, 1905. Alfred THauss, New York. (Elberfeld.) 
New azo dye. 


3'/-Amino phenyl 5-oxy 7-sulfo 1.2-NAPHTHIAZOLE. 
3-Nitro BENZALDEHYDE combined in hot aq. with 2-AMINO 5-NAPHTHOL 7-sulfo then refluxed 
with Na,S and S. 


797,441—Aug. 15, 1905. Re. 12,557—Nov. 13, 1906. 
Thilo KroEBER and Carl JAGERSPACHER, Switzerland. (Basle.) 
Azo dye and process of making same. 


1-Amino 2-NAPHTHOL 4-sulfo, or other, acetylized below o°, neut., NaNO, added then HCl 
in bulk, the resulting magma of diazo salt added to 1.6-dioxy NAPHTHALENE or other, in alk. soln. 
Violet color first produced changes to blue, as the acetyl group which enters OH is easily saponi- 
fied. Rep, BLUE, to BLACK acid and developed (CrO,) dyes. 

In D. R. P. 155,083 diazotization takes place in organic acid soln. but large amounts of 
naphthoquinone form. 


797,731—Aug. 22, 1905. Martin Herzperc, New York. (Elberfeld.) 
Black azo dye. 


3-Nitro acetyl 4-PHENYLENE DIAMIN coupled with 1-ethoxy 8-NAPHTHOL 3.6-disuifo, or other 
and saponified. Bnacx and rep (acetyl comp.) acid dyes. 
Addition to 792,032. 


797,732—Aug. 22, 1905. Martin Herzperc, New York. (Elberfeld.) 
Black azo dye. 
3-Nitro acetyl 4-PHENYLENE DIAMIN, coupled with ethyl 1-aAmIno 8-NAPHTHOL 3.6-disulio or 


other, and saponified. Buiack and rep (acetyl comp.) acid dyes. 
Near S. 64—‘‘Azo Acid Red B.” Addition to 792,032. 


798,098—Aug. 29, 1905. Fritz Carl GunTHER, Germany. (Badische.) 
Yellowish azo dye. ‘ 


SULFANILIC acid, or other, coupled in acetic or alk. soln. with 2.6-diamino 1-chlor BENZENE 
4-sulfo. Yellow acid dyes. 


798,808—Sept. 5, 1905. August Leopold Lasxa, Germany. (Oehler..) 
Blue azo wool dye and process of making same. 


6-Nitro 2-amino PHENOL 4-sulfo coupled with 2-oxy NAPHTHOIC acid. BuiueE acid dye that 
leaves cotton effect threads undyed. 


800,914—Oct. 3, 1905. Wilhelm Herzperc, Germany. (Berlin.) 
Yellow red azo dye. 


4-NITRANILIN 2-sulfo or other, coupled with 2.7-dioxy NAPHTHALENE, product suspended in 
aq. containing 1 mol. NaOH together with toLuENE 4-sulfo chloride. Rep, vari-colored lakes, 
(Ba, Al) fast to light, water and oil. ; 


803,592—Nov. 7, 1905. Wilhelm Herzperc and Otto SrepErRT, Germany. (Berlin.) 
Monoazo dye and process of making same. 


Acetyl 4.2-diamino PHENOL 6-sulfo, coupled with 2-NAPHTHOL, or other, then saponified. 
Essentials are that first component shall contain a free or only partly substituted amino group and 
second component a naphthol, or deriv. with sulfo or second OH group. Rep and BLAcK acid 
and developed (CrO,) dyes, fast to washing, milling, potting and light. 


805,918—Nov. 28, 1905. Re. 12,555—Nov. 13, 1906. Thilo Krorser, Switzerland. (Basle.) 
Monoazo dye and process of making same. 


I-AMINO 2-NAPHTHOL 4-sulfo, dissolved in alk., acetylated at 0° NaNO, added then HCl in 
bulk and yellow cryst. magma of diazo component added to alk. soln. of 1.8-dioxy NAPHTHALENE 
3.6-disulfo. Other components claimed. 

Addition to 797,441. 


806,077—Nov. 28, 1905. Ernst FussENEGGER, Germany. (Badische.) 
Azo coloring-matter. 


ANILIN or other, coupled with 1.5-dihydroxy QUINOLIN. YELLOW tO ORANGE RED direct dyes, 
suitable for lakes. 


GROUP VI.—AZO 139 


806,415—Dec. 5, 1905. Re. 12,556—Nov. 13, 1906. Thilo KrorsEr, Switzerland. (Basle.) 
Blue azo dye and process of making same. 


I-AMINO 2-NAPHTHOL 4-sulfo, or other, acetylated and coupled with 1-NAPHTHOL 5- or 4-sulfo. 
Rep and BLUE acid and developed (CrO,) dyes. 
Near S$. 180—‘‘Erio Chrome Blue Black B.’”? Addition to 797,441. 


807,119—Dec. 12, 1905. Felix KiincEMANN and Georg KaniscHEer, Germany. (Cassella.) 
Red azo dye and process of making same. 


5-Oxy 7-sulfo 1.2-NAPHTHIMIDAZOL with N and C substituted respectively by the benzyl and 
benzylidine rests of amino benzaldehyde azo 2-naphthol sulfo. 

3-Amino BENZALDEHYDE coupled with 2-NAPHTHOL 6-sulfo, 2 mols. of product boiled in dil. 
sod. acetate soln. to condense with 1 mol. 1.2-diamino 5-NAPHTiI0L 7-sulfo, again boiled in HCl 
soln. with diazo ANILIN, or other. Rep direct dyes. 


807.289—Dec. 12, 1905. Thilo KroreBer, Switzerland. (Basle.) 
Brown azo dye and process of making same. 


Prcramic acid, or other ortho amino phenol, coupled in acetic or alk. carb. soln. with 2.4- 
diamino DIPHENYLAMIN 3/-sulfo from 1.3-dinitro 4-chlor BENZENE, 2nd METANILIc or sulfanilic acid 
by condensation and reduction Brown acid mordant dyes, fast to light, fulling and copper. 


807,422—Dec. 12, 1905. Karl Biesricu, Germany. (Kalle.) 
Zine azonaphthol and process of making same. 


Nitroso NAPHTHOL treated with bisulfite and HCl to form 1-AMINO 2-NAPHTHOL 4-sulfo which 
with ZnSO,, a little Zn(OH), and NH,, then NaNO, forms diazo oxid that couples readily with 
2-NAPHTHOL on heating to 40-45° in alk. soln. Rep, vioLET and BLACK direct and developed 
(CrO,) dyes 

S. 181—‘‘Palatin Chrome Black 6B.” Note 770,177. 


813,155—Feb. 20, 10906. Georg KatiscHerR, New York. (Cassella.) 
Red azo dye and process of making same. 


2-TOLUIDIN coupled in alk. soln. with 3’.3”-diamino dibenzal 1.2-DIAMINO 5-NAPHTHOL 7-sulfo, 
derived by condensation of 1.2-DIAMINO 5-NAPHTHOL 7-sulfo. with 2 mols. 3-amino BENZALDEHYDE. 
Rep direct and developed (coupled) dyes, that can be diazotized on fiber. 


8$18,981—Apr. 24, 1906. Franz ScuHotL, Germany. (Hochst.) 
Yellow dye and process of making same. 


2-Amino SALICYLIC acid or other, coupled in alk. soln. with ethyl aceto acetic ester or other 
aliphatic beta diketone or ketone aldehyde. Green YELLOW acid mordant (Cr, Cu) dye, suitable 
for lakes, and fast to light. 


8$20,052—May 8, 1906. Richard KircuHorr and Leo Kerxkovius, Germany. (Berlin.) 
Violet-color lakes and process of making same. 


4'-Amino phenyl 3.8-disulfo 1.2-NAPHTHYL triazol, coupled with 2-NAPHTHOL 3.6-disulfo heated 
to 80-90°, pptd. by aq. BaCl,, or other alk. earth salt with Al(OH), paste added for substratum. 
Vio.er lakes, fast to light, and aq. 


823,793—June 109, 1906. Thilo Krorser, Switzerland. (Basle.) 
Disazo dye and process of making same. 


2.4-Diamino PHENOL, coupled in acetic soln. with 1-NAPHTHOL 4-sulfo and in alk. soln. with 
2-NAPHTHOL. Other components claimed. Brown, vioLET and BLAcx acid and developed (CrO,) 
dyes, fast to milling, washing, potting and light. 


8$26,279—July 17, 1906. Kar] ScHIRMACHER and Friedrich Scumipt, Germany. (Hochst.) 
Ortho-oxyazo dye. 


2-Amino PHENOL, coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo. BiLurE or rep acid mor- 
dant or acid dyes. 
Note 826,280 to 82 and 827,468. 


826,280—July 17, 1906. Karl ScH1IRMACHER and Friedrich ScHmipt, Germany. (Hdéchst.) 
Ortho-oxymonoazo dye. 


4-Chlor 2-amino PHENOL coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo. Buiur or rEp acid 
and acid mordant (Cr) dyes. 
Addition to 826,279. 
10 


140 DIGEST OF PATENTS 


826,281—July 17, 1906. Friedrich ScumMipt and Karl ScutrmMaAcHER, Germany. (Ho6chst.) 
Ortho-oxymonoazo dye. 
6-Amino 4.2-xyLENoL (OH —1) coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo. Biux and 


RED acid and mordant (Cr) dyes. 
Addition to 826,279. 


826,282—July 17, 1906. Friedrich Scumipt and Karl ScuiRMAcHER, Germany. (Ho6chst.) 
Ortho-oxyazo dye. 
2-Amino 4-cRESOL, coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo. Rep and siuxE acid and 


acid mordant (Cr) dyes. 
Addition to 826,279. 


827,468—July 31, 1906. 

Karl ScuirMACHER, Friedrich ScumMipt, Carl Pretzety, and Willy ScHumacHER, Germany. 

(Hochst.) 

Ortho-oxymonoazo dye and process of making same. 

5-Nitro 2-amino PHENOL, coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo, in presence of 
hydroxide of Mg. Ba, Sr, Ca, Zn. Other components claimed. Rep to violet-sLug acid and acid 
mordant (Cr) dyes. 

Near S. 87—‘‘Peri Wool Blue B.’’ This is the generic patent, for specific claims note 
826,279 to 82. 


830,312—Sept. 4, 1906. Otto Ernst, Germany. (Hochst.) 
Red lake. 


3.4-Dichlor ANILIN 6-sulfo, obtained by nitrating and reducing 3.4-dichlor BENZENE 6-sulfo 
or by sulfonating 3.4-dichlor ANILIN, coupled with 2-NapruoL 3.6-disulfo. Yellow rep lakes, fast 
to light and aq., for wall paper, lithography, printers colors, etc. 


8$32,393—Oct. 2, 1906. August Leopold Lasxa, Germany. (Griesheim.) 
Black polyazo dye and process of making same. 


ToLipIN or other, coupled with 2-amino 8-NAPHTHOL 6-sulfo or deriv., tetrazotized and 
coupled in alk. soln. with 1 mol. dye from 4-NITRANILIN 2-sulfo azo 2-AMINO 5-NAPHTHOL 7-sulfo 
(coupled in acid solution) and 1 mol. 3-PHENYLENE DIAMIN, or other, then nitro group reduced 
by Na,S. siacxk direct dye, fast to washing, that can be diazotized on fiber. 

Near S. 491—‘‘Dianil Black PE.” 


833,605—Oct. 16, 1906. Paul Juxtius, Germany. (Badische.) 
Bluae-red azo dye. 


MeETaAnitic acid, or other aromatic amino sulfo acid, (19 tabulated), coupled with ethyl 
ether of 1.4-dioxy NAPTHALENE, derived from 1.4-dioxy NAPHTHALENE, alcohol and mineral acid, 
or other alkyl ethers of same. 

Near S. 146—‘‘Azo Fuchsin G.”’ 


835,539—Nov. 13, 1906. Thilo Krorser, Switzerland. (Basle.) 
Monoazo dye and process of making same. ; 


I-AMINO 2-NAPHTHOL 4-sulfo or other, coupled with 1-NAPHTHOL using alcohol, pyridin, anilin 
etc., as solvents. VuioLEer and sack acid and developed (CrO,) dyes, which when chromed are 
fast to milling, washing and light. 

S. 180—‘‘Erio Chrome Blue Black B.’’ 


837,128—Nov. 27, 1906- Karl ScuH1irRMACHER, Germany. (Hoéchst.) 
Azo dye and process of making same. 


ANTHRANILIC acid coupled with 2-NnaPHtTHOL, 6-sulfo. Rep lakes, fast to light. 
S. 201—‘‘Pigment Scarlet G.” 


837,736—Dec. 4, 1906. Arnold ScHEpLER, Switzerland. (Basle.) 
Red azo dye and process of making same. 


4/-Amino phenyl 1.2-NAPHTHIMIDAZOLE 5-oxy 7-sulfo combined in alk. soln. with diazo 2- 
TOLUIDIN or other aromatic amin or deriv., diazotized and again coupled with NAPHTHIONIC acid, 
or other. Orange to violet-rEp direct dyes, fast to light. 


GROUP VI.—AZO 141 


839,360—Dec. 25, 1906. Wilhelm Bauer, Germany. (Bayer.) 
Red disazo dye. 
4.'4.”-Diamino diphenyl diether of HyDROQUINONE coupled in alk. carb. soln. with 2 mols. a- 


AMINO 5-NAPHTHOL 7-Sulfo, or one mol. of this and one of another coupling agent. Other com- 
ponents claimed. Rep direct dye, fast to acids. 


839,382—Dec. 25, 1906. Oscar GuntuerR, Germany. (Bayer.) 
Red azo dye. 
4.4’-Diamino diphenyl glycol coupled with 2 mols. 2-AMINO 5-NAPHTHOL 7-sulfo, or 1 mol. 


of this with other coupling agent, (list of 21 given). Orange to violet rep direct dyes, fast to 
acids, that can be diazotized on fiber. 


$39,489—Dec. 25, 1906. August Leopold Lasxa, Germany. (Griesheim.) 
Black mordant dye and process of making same. 


I-AMINO 2-NAPHTHOL 4-sulfo coupled with 3-oxy DIPHENYLAMIN or homologs. Brack and 
VIOLET, acid and developed (CrO,) dyes, fast in all respects. 


839,605—Dec 25, 1906. Adolf KucHEnBEcKER, Germany. (Hochst.) 
Yellow azo dye. 


3-XYLIDIN 6-sulfo coupled with 4-sulfo phenyl PyRAZOLONE carbo acid, ot other. Green 
YELLOW acid dye, fast to light. 


8§41,371—Jan. 15, 1907. Melchior Bontcrr, Switzerland. (Sandoz.) 
Azo dye and process of making same. 

4-Nitro 2-amino PHENOL or deriv., coupled with phenyl 1-NAPHTHYLAMIN 8-sulfo or other 
aryl. deriv. thereof. Vari-colored acid and acid mordant (Cr, Cu) dyes, fast to light, acids, alks. 
and milling. 

S. 8s5—“‘Omega Chrome Black.” 


842,048—Jan. 22, 1907. Hugo Wirtrer, Germany. (Bayer.) 
Red tetrazo dye. 


BENzIDIN coupled in acid soln. with 1 mol. each of 2-NAPHTHYLAMIN 3.6-disulfo and 2-AMINO 
8-NAPHTHOL 6-sulfo. Blue rep direct dye. 
S. 332—‘‘Benzo Fast Red 9 BC.” 


842,548—Jan. 29, 1907. Wilhelm Herzzperc, Germany, (Berlin.) 
Azo dye and process of making same. 


DIANISIDIN, or homologs, sulfonated to diortho disulfo product then coupled with 2 mols. 
2-NAPHTHOL. Other components claimed. Blue rep acid dye, fast to washing and milling. 


843,077—Feb. 5, 1907. Oscar DresseL and Myrtil Kaun, Germany. (Bayer.) 
Azo dye. = 
s-Nitro 4-chlor 2-amino PHENOL, coupled with NaPHTHIONIC acid or other sulfo acid of naph- 


thol amin (list of 14). Rep to vIOLET or GREEN to blue to black acid and developed (CrO,) 
dyes. 


843,137—Feb. 5, 1907. Oscar DresseL and Anton OssenBEcK, Germany. (Bayer.) 
Azo dye. 

4-Nitro 2-amino PHENOL or other non sulfonated nitro ortho amino phenolic comp., coupled 
with phenyl 2-AMINO 5-NAPHTHOL 7-sulfo or homologs. RED to VIOLET or BLUE to black acid and 
developed (CrO,) dyes. 

Note 843,149 and 843,756. (1) 


843,149—Feb. 5, 1907. Myrtil Kaun and Richard Kotus, Germany. (Bayer.) 
Azo coloring-matter. 


6-Nitro 4-chlor 2-amino PHENOL coupled with phenyl 2-AMINO 5-NAPHTHOL 7-sulfo or homo- 
logs. WiIOLET to RED or BLUE to BLACK acid and developed (CrO,) dyes. 
Addition to 663,137. 


142 DIGEST OF PATENTS 


843,756—Feb. 12, 1907. Richard Korur and Anton OssenBEcK, Germany, (Bayer.) 
Azo coloring-matter. 


4-Chlor 2-amino PHENOL, or other non-sulfonated chlor ortho amino phenolic comp., coupled 
with phenyl 2-AMINO 5-NAPHTHOL 7-sulfo, or like compound. RED to VIOLET or BLACK acid and 
acid mordant (Cr) dyes. i 

Addition to 843,137. 


843,808—Feb. 12, 1907. Karl HacgEMANN and Otto Stance, Germany. (Bayer.) 
Black azo dye and process of making same. 
I-AMINO 8-NAPHTHOL 3.6-disulfo or other, condensed with ANILIN or other aromatic amin to 


form aryl amino comp. then combined in alk. soln. with diazo 4-NITRANILIN or other. Brack 
acid dye. 


8§44,814——Feb. 19, 1907. Thilo Krorsrer, Switzerland, (Basle.) 
Monoazo dye and process of making same. 


NAPHTHOL YELLOW S reduced to mono amino compound, diazotized and coupled with 2- 
NAPHTHOL or other coupling agent. Bunack or BLUE acid and developed (CrO,) dyes, fast when 
after chromed. 


844,845—Feb. 109, 1907. Max Brcxr, Germany, (Hoéchst.) 
Yellow and orange pigment colors. 


NAPHTHYLAMIN, anilin or other unsulfonated amins, homologs or derivs. coupled with PyYRA- 
ZOLONE, its derivs and homologs. ORANGE to YELLOW dye suitable for lakes, as non poisonous 
substitutes for chrome yellow and other yellow to orange mineral pigments. 


846,511—Mar. 12, 1907. Willy ScHuMACHER, Germany. (Hochst.) 
Ortho-oxy monoazo dye. 


s-Nitro 4-chlor 2-amino PHENOL coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo. Green 
blue to RED acid and acid mordant (Cr) or developed (CrO,) dyes, fast to light. 


849,690—Apr. 9, 1907. August Leopold Lasxa, Germany. (Griesheim.) 
Yellow wool-dye. (Process also claimed.) 

4-TOLUIDIN 3-sulfo coupled with 4’-sulfo phenyl PyRAZOLONE carbo. acid, or other pyrazolone. 
YELLow acid dye, faster to light than isomers, adapted for lake colors. 

Note 849,739. 


849,739—Apr. 9, 1907. August Leopold Lasxa, Germany. (Griesheim.) 
Yellow monoazo dye and process of making same. 


3-4-Dichlor ANILIN 6-sulfo or other chlor amino sulfo acid coupled with 4’-sulfo phenyl PyrA- 
ZOLONE carbo, or other pyrazolone. YELLOW acid dye, fast to light and suitable for lakes. 
Addition to 849,690. 


858,065—June 25, 1907. Otto Ernst and Gillis GuLLBRANsson, Germany. (Ho6chst.) 
Monoazo dye for lakes and process of making same. 


2-NAPHTHLAMIN 1-sulfo coupled with 2-oxy 3-NAPHTHOIC acid. Blue rep dyes for lakes, fast 
to light and aq., useful for book and tin-printing, lithography and oil painting. 
S. 179.—‘‘Lake Bordeaux B.”’ Note 650,757. 


858,444—July 2, 1907. Oscar DressEL and Richard Korner, Germany. (Bayer.) 
Black azo dye. 


4-PHENYLENE DIAMIN 4ZO 2-AMINO 8-NAPHTHOL 6-sulfo “Gamma,” coupled with 2 mols. 3-amino 
PHENYL glycin, or homolog, or with 1 mol. of this and 1 mol. of 3 or 4-PHENYLENE DIAMIN or 
other (list of 22). BLACK direct dyes. 

Note 859,950. 


859,930—July 16, 1907. Oscar DressELi and Richard Kotur, Germany. (Elberfeld.) 
Bluish black azo dye. 

Acetyl 4-PHENYLENE DIAMIN coupled in alk. carb. soln. with 2-AMINO 5-NAPHTHOL 7-Sulfo, 
acetyl group removed by boiling in dil. NaOH, and azo comp. tetrazotized and coupled with 2 


GROUP VI.—AZO 143 


mols. 3-amino phenyl GLycin or one mol. of this and one mol. of 3-PHENYLENE DIAMIN or other. 
Blue sBiack direct dyes. 


860,220—July 16, 1907. August Leopold Lasxa, Germany. (Griesheim.) 
Blue cotton dye and process of making same. 


DIANISIDIN, or other diamino base, coupled with 1 mol. each of 1.8-dioxy NAPHTHALENE 3.6- 
disulfo, or other peri dioxy sulfo acid, and phenyl 2-aMINO 5-NAPHTHOL 7-sulfo or other. Buus 
direct dye, fast to alk. carb. 

Note 860,221. 


860,221—July 16, 1907. August Leopold Lasxa, Germany. (Griesheim.) 
Blue disazo-dye and process of making same. 


DIANISIDIN or other diamino base, coupled with 1 mol. each of 1-NAPHTHOL 3.6-disulfo or 
isomers, and phenyl 2-AMINO 5-NAPHTHOL, 7-sulfo or other. BLur to vioLEet direct dye, fast to 
alk. carb. 

Addition to 860,220. 


860,575—July 16, 1907. Conrad Scurause and Erhart ScuieIcHER, Germany. (Badische.) 
Azo dye. 


4 or 5-Chlor 2-NITRANILIN coupled with 2-NAPHTHOL. Other components claimed. 
ORANGE to RED lakes, fast to light, oil, lime and aq. 
Note 865,587. 


863,290—Aug. 13, 1907. August Leopold Lasxa, Germany. (Griesheim.) 
Black mordant azo dye. (Process also claimed.) 


4-Chlor 2-amino PHENOL, or 2-amino phenol homologs or derivs. containing not more than 
one NO, group, coupled with 2.8-dioxy NAPHTHALENE 6-sulfo, in presence of Ca(OH),. Rep and 
BLACK acid and developed (CrO,) dyes, fast to milling, potting and light. 


8$63,396—Aug. 13, 1907. Carl ImMmMERHEISER, Germany. (Badische.) 
Coloring-matter lake. 


Amino azo BENZENE, or toluene, coupled with 1-NAPHTHOL 4-sulfo, pptd. in company with 
Al(OH), and BaCl,. Rep lakes, fast to light. 
S. 224—“Cloth Red G.”’ 


865,252—Sept. 3, 1907. Myrtil Kaun and Richard Kotut, Germany. (Bayer.) 
Azo dye. 


4-Chlor 2-amino PHENOL 6-sulfo, coupled with 1-NAPHTHOL 5-sulfo. Violet RED to BLHE acid 
and developed (CrO,) dyes. 
' Note 865,253. 


865,253—Sept. 3, 1907. Myrtil Kaun and Richard Korue, Germany._ (Bayer.) 
Azo dye. 


4-Chlor 2-amino PHENOL 6-sulfo coupled with NAPHTHIONIC acid. ReEpD to vioLet, acid and 
acid mordant (Cr) dyes. 
Addition to 865,252. 


865,587—Sept. 10, 1907. Wilhelm Herzserc and Oscar SPENGLER, Germany. (Berlin.) 
Red-orange monoazo dye and process of making same. 


2-Chlor 4-NITRANILIN coupled with 2-NAPHTHOL. Orange RED lake dye, fast to light, aq., alc., 
oil, adapted for chromolithography, paper staining and wall paper painting. 
Note 860,575. 


873,798—Dec. 17, 1907. Rudolf ScHuise, Germany. 
Red azo dye and process of making same. 


3-Amino BENZALDEHYDE condensed with 1.2-DIAMINO 5-NAPHTHOL 7-sulfo to form 1I-NAPH- 
THIMIDAZOLE by boiling in bisulfite soln. then combined with diazo ANILIN, or other, diazotized 
and coupled with 2-NaPHTHOL 6-sulfo, or other. Rep direct dye, fast to washing, light and acids. 


144 DIGEST OF PATENTS 


874,967—Dec. 31, 1907. Walter Konic, Germany. (Bayer.) 
Greenish black azo dye. 


I-NAPHTHYLAMIN 5-Sulfo or other, coupled with methyl 1-AMINO 7-NAPHTHOL or other. Brack 
acid dyes, fast to washing, cotton not dyed in mixed goods. 
Note 874,968. 


874,968—Dec. 31, 1907. Walter Konic, Germany. (Bayer.) 
Violet-black azo dye. 


NAPHTHIONIC acid or other, coupled with 1-AMINO 7-NAPHTHOL. Black acid dye. 
Addition to 874,967. 


877,643—Jan. 28, 1908. Oscar GuNTHER and Leopold Hrsst, Germany, (Bayer.) 
Azo dye. 


I-AMINO &-NAPHTHOL 3.6-disulfo or other, coupled with 1I-NAPHTHYLAMIN or other amin, 
rediazotized and coupled with phenyl 2-AMINO 5-NAPHTHOL 7-sulfo (list of 26 combinations with 
color of dyes). BLur or VIOLET to violet RED direct dyes. 


877,644—Jan. 28, 1908. Oscar GUNTHER and Leopold Hrsst, Germany. (Bayer.) 
Azo dye. 

I-AMINO 8-NAPHTHOL 3.6-disulfo “‘H,’ or sulfurus acid ester, the acetyl or aryl sulfo ester, 
etc., coupled with 4-xYLIDIN, or other suitable amin, again diazotized and coupled with 2-AMINO 
5-NAPHTHOL 7-sulfo. Violet RED to VIOLET or BLUE direct dyes. 

Addition to 877,643. 


878,964—Feb. 11, 1908. Karl Konic, Germany. (Héchst.) 
Red color-lake. : 
2-Amino BENzoOIC acid coupled with 2-NaPHTHOL. Rep lakes, excellent covering power in 


oil, fast to alc., aq., light and lime. 
S. 200—‘“Lake Red D.” 


879,053—Feb. 11, 1908. Paul Jutius and Ernst FussENEGGER, Germany. (Badische.) 
Azo dye and process of making same. 

2.5-Dichlor ANILIN, I-naphthylamin 5-sulfo or other, coupled with triphenyl methane product 
from tetra methyl diamino BENZHYDROL condensed with 2.6-dinitro DIPHENYLAMIN 4.3/-disulfo or 
(2.4.6.3’) and reduced, to form 2/.6’-diamino 4’-sulfo phenyl 4-amino 2-sulfo tetra methyl diamino 
triphenyl methane. YELLOW, BROWN, GREEN and BLUE acid and developed (CrO,) dyes. 


879,424—Feb. 18, 1908. Nathan SuLzBEeRcER, Germany. (Berlin.) 
Process of making azo dyes containing radicals of higher fatty acids. 


STEARIC ACID ANILID or amid of any fatty acid nitrated, reduced in alc. soln. and resulting 
4-amino stearic acid ANILID coupled with 2-NAPHTHOL or other. RED, YELLOW, BROWN and VIOLET 
basic dyes, soluble in alcohol, wax, fats, paraffin, etc., used for cosmetics, colored soaps, candles, 
pigments and artists’ colors, can be melted and cast in sticks, stable to acids and alkalies, without 
smell or taste, will not become rancid. 

Note 902,021. 


879,552—Feb. 18, 1908. Georg KaLiscHER, New York. (Cassella.) 
Brown azo dye and process of making same. 

Dinitro chlor BENZENE or other, condensed in alk. soln. with PHENOL 4-sulfo, naphthol sulfo, 
or other, reduced to 2.4-diamino 4-sulfo DIPHENYL ether, then coupled with diazo 4-nitro 2-AMINO 


PHENOL or other ortho amino phenol or naphthol deriv. ORANGE to RED to BROWN acid and 
developed (CrO,) dyes, fast to washing, milling, and light. 


880,292—Feb. 25, 1908. Hugo GELDERMANN, Germany. (Berlin.) 
Red azo dye and process of making same. _ (Process not claimed.) ; 
4’-Sulfo 2.4-diamino PHENYL ether,* sulfonated to disulfo comp. diazotized and coupled with 
2 mols. 2-NAPHTHOL. RED acid dyes, fast to milling. 
* For information about ether, see Ber. 29, 1446, also 879,552. 


GROUP VI.—AZO 145 


880,293—Feb. 25, 1908. Hugo GELDERMANN, Germany. (Berlin.) 
Yellow tetrazo dye and process of making same. (Process not claimed.) 
Thio ANILIN disulfo,* coupled with 2 mols. PHENOL, or homologs, and alkylated with Etuy4, 


bromide or similar salts. YxELLow acid dye, fast to milling, will not bleed into cotton. 
* Note information about thio anilin in Ber. 39, 611. 


886,985—May 5, 1908. Georg KatiscHer, New York. (Cassella.) 
Red trisazo dye and process of making same. 

1.2-DIAMINO 5-NAPHTHOL 7-sulfo, combined with 2 mols. 3-amino BENZALDEHYDE to form 5-oxy 
7-sulfo 1.2-NAPHTHIMIDAZOLE, substituted in C and N positions by 3-amino phenyl and 3-amino 


benzyl respectively, combined in alk. soln. with diazo ANILIN, or other, then tetrazotized and 
coupled with 2 mols. 2-NAPHTHOL 6-sulfo. Rep direct dyes fast to washing and acids. 


887,348—May 12, 1908. Karl ScHNITzSPAHN, Germany. (Griesheim.) 
Mordant azo dye and process of making same. 


6-Nitro 2-amino 4-CRESOL, or other ortho amino phenol deriv., coupled with phenyl 1-NAPH- 
THYLAMIN 6- or 7-sulfo, or other aryl deriv. of same. RED or VIOLET to BLACK acid or developed 
(CrO,) dyes, fast to milling when chromed. 


888,036—May 109, 1908. Christopher Ris and Ernst HaacEer, Germany. (Jager.) 
Blue disazo dye. 


D1aANIsIDIN, homologs or derivs., coupled with 1 mol. each of 2-NAPHTHOL 6-sulfo, and 1- 
AMINO 8-NAPHTHOL 4-sulfo. Briur direct and developed (Cu) dyes, fast to milling, and when 
coppered also fast to light. 

S. 384—‘“Chicago Blue 2R’’ and 420—‘‘Azidin Wool Blue B.” 


888,522—May 26, 1908. Emil Meyrr, Germany. (Bayer.) 
Red tetrazo dye. 


2.2'-Dichlor BENZIDIN coupled with 2 mols. 2-NAPHTHOL 3.6-disulfo “R.’’ Rep direct dye, 
fast to light and milling. 


888,837—RMay 26, 1908. Carl Oscar Mutter and Alexander Orro, Germany. (Hochst.) 
Red azo dye. (Process also claimed.) 


ANILIN, or other, coupled with 4-amino benzoyl 2-AMINO 5-NAPHTHOL 7-sulfo, then coupled 
in alk. soln. with 2-AMINO 5-NAPHTHOL 7-sulfo, its acetyl deriv., or the urea formed by heating 
it in dil. acetic soln. with KCNO. Rep direct dye.. 


§88,981—May 26, 1908. Otto Ernst and Carl Prerzery, Germany, (Héchst.) 
Making red azo dye lakes. (Product, not process, claimed.) 


2-NITRANILIN coupled with 2-NAPHTHOL 6-sulfo, and pptd. as pigment by CaCl,, BaCl, or BaCl, 
and Al(OH), together, etc. Red ORANGE lakes, fast to light, oil and aq. 
Near S. 148—‘“‘Fast Orange O.”’ 


889,016—May 26, 1908. Karl Jepticxa and Arnold ScHEDLER, Switzerland. (Basle.) 
Red tetrazo dye. (Process also claimed.) 


3.3'-Diamino azoxy BENZENE from 3-NITRANILIN, or other azoxy amin, coupled with 2 mols. 
3/-amino benzoyl 2-AMINO 5-NAPHTHOL 1.7-disulfo or other amino aryl, acetyl amino naphthol 
sulfo acids and mixtures thereof. Rep direct and developed coupled dyes, fast to washing and 
can be developed on fiber by 2-NAPHTHOL. 


891,931—June 30, 1908. Carl HEIDENREICH, Germany. (Bayer.) 
Blue azo dye. 

3-Chlor 4-nitroso dimethyl] an1~1n reduced to 4-amino 3-chlor dimethyl aniz1n or other, and 
coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo. Biux acid dyes, fast to alkalies and light. 


897,529—Sept. 1, 1908. Oscar GUNTHER and Leopold Hrssr, Germany. (Bayer.) 
New disazo dye. 

I-AMINO 8-NAPHTHOL sulfurus acid ester, or other suitable amin, coupled with 2-amino ethyl 
4-crEso. (OH —1), or other suitable amin, saponified, coupled again with 2-AMINO 5-NAPHTHOL 
1.7-disulfo or deriv. V10LET to BLUE direct dyes. 

Note 808,217. 


146 DIGEST OF PATENTS 


898,217—Sept. 8, 1908. Oscar GuntuerR and Leopold Hrssz, Germany. (Bayer.) 
New disazo dye. 


3-Chlor 4-nitroso dimethyl an1z1n reduced to 4-amino 3-chlor dimethyl anizin, or other, 
suitable amin, saponified and again coupled with 2-AMINO 5-NAPHTHOL 7-sulfo. Other compo- 
nents claimed. Buus to vioLeT direct dyes, fast to light. 

Addition to 897,529. 


899,171—Sept. 22, 1908. W. Konic, Germany. (Elberfeld.) 
Azo dye. 


I-NAPHTHYLAMIN homologs or derivs. coupled with 1-AMINO 7-NAPHTHOL 4-sulfo or alkylated 
derivs. A VIOLET to BLACK acid dye, fast to washing. 


901,675—Oct. 20, 1908. M. Bonicer, Switzerland. (Sandoz.) 
Yellow azo dye and process of making same. 


METANILIC acid coupled in alk. soln. with 2’.5’-dichlor 4’-sulfo phenyl methyl pyRAzoLONE or 
other. A green-YELLOW acid dye, fast to light, suitable for lakes. 
S. 22—‘‘Xylene Yellow 3G.” — 


902,021—Oct. 27, 1908. N. Suuzpercer, New York. 
Process of making azo dyes containing fatty acid radicals. 


SrEaRIc acid and ANILIN, condensed to form anilid which is nitrated, one or more mols., 
then reduced to amino stearic acid aniLip, which is combined with diazo ANILIN, or other. 
Phenylene diamin instead of anilin, condensed with stearic acid gives amino anilid directly. 
Other components claimed. YELLOW, RED or BROWN basic dyes, suitable for lakes. 

Addition to 879,424. 


902,186—Oct. 27, 1908. P. VotKmann, Germany. (Elberfeld.) 
Azo dye. 


ANILIN, coupled with 2 mols. 4’.8’-disulfo 2-naphthyl methyl PyRAzoLoNE or one mol. of 
this and 1 mol. of saLicyntic acid. Other components claimed. A YELLOW, RED, ORANGE, or 
BROWN acid and direct dye, fast to light. 


903,284—Nov. 10, 1908. A. Gressty, Germany. (Cassella.) 
Orange or brown dye and process of making same. 


Dinitro sTILBENE disulfo or other heated in alk. soln. with SULFANILIC acid azo I-NAPHTHY- 
LAMIN or other. A RED, ORANGE, Or BROWN direct fast dye. 


906,421—Dec. 8, 1908. W. HeErzperc and O. SpENGLER, Germany. (Berlin.) 
Ortho-oxy-monoazo dye and process of making same. 


PicraMic acid coupled with 2-NAPHTHOL 6-sulfo, neutralized with lime and treated with 
calcium hydrosulfid (from sod. sulfid and CaCl,) to reduce one nitro to an amino group. <A 
BROWN tO BLACK, olive-GREEN or brown-REpD acid and developed (CrO,) dye, fast to milling and 
potting. 


906,422—Dec. 8, 1908. W. Herzserc, Berlin, and H. Oster, Germany. (Berlin.) 
Yellow monoazo dyestuff. 


2-Chlor ANILIN, or other, coupled with 3-PHENYLENE DIAMIN 2.5-disulfo. A yELLOWw acid dye, 
fast to acids, alks. and light. 


908,580—Jan. 5, 1909. W. Konic, Germany, (Merz.) 
Monoazo dye and process of making same. 


2-NAPHTHYLAMIN 8-sulfo coupled with 2-oxy 3-NAPHTHOIC acid. A violet-rED dye, suitable 
for lakes, (Ba, Ca, Pb, etc.) fast to water, oil and alc. 


911,186—Feb. 2, 1909. E. Unricus, Germany. (Wiilfing.) 
Red mono-azo dye. (Process also claimed.) 


2-NAPHTHYLAMIN 1-sulfo coupled with 2-NAPHTHOL in presence of Turkey Red oil, or other. 
A RED dye suitable for lakes fast to aq., alc., oil, and lime. 
Near S. 115.—‘‘Azo Turkish Red.”’ Note 910,03¢. 


GROUP VI.—AZO 147 


912,138—Feb. 9, 1909. R. Laucu, Germany. (Berlin.) 
Orange lake dye and process of making same. (Process not claimed.) 


2.4-DINITRANILIN coupled with finely divided 2-NAPHTHOL. An ORANGE dye suitable for 
lakes (Ba, Al) fast to light, lime, oil, aq., alc., acids and alk. 


912,182—Feb. 9, 1909. R. Scuu.t, Germany. (Cassella.) 
Red cotton dye and process of making same. 
SULFANILIC acid coupled in alk. soln. with 3’-amino phenyl dihydro 1.2-NAPHTHIMIDAZOLE 5- 


oxy 7-sulfo, then coupled with a second mol. of same in alk. soln. A RED direct and developed 
dye, that can be coupled on fiber and then is fast to washing and acids. 


912,356—Feb. 16, 1909. A. BErepoutt, Germany. (Elberfeld.) 
Azo dye. 
I-AMINO 8-NAPHTHOL sulfurous acid ester, coupled in acetic soln. with 1.8-dioxy NAPHTHALENE 


4-sulfo, then saponified by heating in alk. soln. at 50°. A vIoLET and BLACK acid and developed 
(CrO,) dye. 


914,144—Mar. 2, 1909. C. IMMERHEISER, Germany. (Badische.) 
Azo dye and process of making same. 


PRIMULIN, 2 parts, diazotized, fiber passed through soln. then through alk. soln. of one 
part 6.8-dihydroxy QuINOLIN. AN ORANGE developed dye. 


914,146—Mar. 2, 19009. P. Juuius and E. Fussgenrccrer, Germany. (Badische.) 
Azo dye and process of making same. 


5-Chlor 2-NITRANILIN 4-sulfo coupled with 2-NAPHTHOL or its sulfo acid. An ORANGE dye 
suitable for lakes, fast to light, alc., lime and heat. 


916,161—Mar. 23, 1900. C. JAGERSPACHER, Switzerland. (Basle.) 
Azo dye and process of making same. 
3-XYLIDIN, 3-azoxy anilin, or other, coupled in alk. soln. with 4’-amino 1/.2’-azimino phenyl 


2-AMINO 5-NAPHTHOL 7-sulfo. Mixed diazo compounds also claimed. A RED or ORANGE direct 
and developed dye, that can be coupled on fiber and then is fast to washing. 


916,323—Mar. 23, 1909. H. Jorpan and W. Neetmeier, Germany. (Bayer.) 
Azo dye. 
DIANISIDIN coupled in alk. soln. with 1 mol. each of acetyl 1-AMINO 8-NAPHTHOL 4.6-disulfo 


and acetyl 4-TOLUYLENE DIAMIN. Other components claimed. A RED to VIOLET or BLUE direct and 
developed (coupled) dye that can be coupled on fiber and discharges white. 


920,151—May 4, 1909. H. Jorpan and W. NEELMEIER, Germany. (Bayer.) 
Trisazo dye 

2-SULFANILIC acid coupled in acetic soln. with 1-NAPHTHYLAMIN 6-sulfo again coupled in 
alk. soln. with 1-NAPHTHYLAMIN 7-sulfo, still further coupled in acetic soln. with acetyl 4.2- 


diamino ANISsoL. Other components claimed. A VIOLET to BLUE direct and developed dye that 
can be coupled on fiber. 


921,105—May 11, 19009. Re. 18,121—June 14, 1910. 
O. GuntTHER and L. Hesse, Germany. (Bayer.) 
Azo dye. 
4-NITRANILIN 2-sulfo coupled with ethyl 2-NAPHTHYLAMIN or other. A VIOLET to BLUE acid 
dye, fast to light, washing and level dyeing. 
Note 921,239. 


921,239—May 11, 1909. O. GuntHER and L. Hrssz, Germany. (Bayer.) 
Azo dye. 
4-NITRANILIN 2-sulfo coupled in acid soln. with 2-AMINO 8-NAPHTHOL 6-sulfo. Other com- 


ponents claimed. A viIoLET to BLACK acid dye, fast to light and washing, and level dyeing. 
Addition to 921,105. 


148 DIGEST OF PATENTS 


921,239—May 11, 1909. Re, 13,122—June 14, 1910. 
O. GunTHER and L. Hesse, Germany. (Bayer.) 


Azo dye. 


4-NITRANILIN 2-sulfo coupled with 2-AMINO 8-NAPHTHOL 6-sulfo in acid soln. Other com- 
ponents claimed. A vioLET to BLACK acid dye, fast to light and washing. 
Near S. 132.—‘‘Lake Red P.” 


921,546—May 11, 1909. 
P. Jutius, E. FussENEGGER and L, BLancry, Germany. (Badische.) 
Azo dye and process of making same. 


4.5-Dichlor 2-NITRANILIN or other ortho nitranilin with chlorin or methyl in both 4 and 5 
positions, diazotized in conc. H,SO,, and coupled in acid soln. with 2-NAPHTHOL. A RED dye 
suitable for lakes, fast to light, heat, oil, acid, alk. and aq. 


924,231—June 8, 1909. J. JANSEN and W. NEELMEIER, Germany. (Bayer.) 
Azo dye. 


4-Nitro 6-amino 2-CRESOL containing nitro or halogen but no sulfo or carbo groups, coupled 
in alk. soln. with 2-AMINO 7-NAPHTHOL. Other components claimed. A sBLAcK acid mordant 
(Cr) and developed (CrO,) dye that may be dyed by one bath method, fast to fulling and light. 
Note 924,232 and 933,842. 


924,232—June 8, 1909. J. JansEN and W. NEELMEIER, Germany. (Bayer.) 
Azo dye. 


Picramic acid, or other ortho amino phenol containing neither sulfo nor carbo groups, 
coupled in alk. soln. with 6.8-dioxy QUINOLIN or other. A RED acid mordant (Cr) and de- 
veloped (CrO,) dye that can be dyed by one bath method. 

Addition to 924,231. 


931,423—Aug. 17, 1909. L. Hesse and O. GunrHeEr, and A. Zart, Germany. (Bayer.) 
Azo dye. 


Amino azo BENZENE sulfo, or other, coupled in alk. soln. with benzoyl 2-AMINO 5-NAPHTHOL 
7-sulfo. Other components claimed. A RED to BLUE direct dye, fast to light. 
Note 931,424. 


931,424—Aug. 17, 1909. Ll. Hrsst, O. GuntueEr, and A. Zart, Germany. (Bayer.) 
Azo dye. 


2-NAPHTHYLAMIN 4.8-disulfo coupled with 4-xYLIDIN, again diazotized and coupled with 
benzoyl 2-AMINO 5-NAPHTHOL 7-sulfo. Other components claimed. A RED to BLUE direct dye, 
fast to light. 

Addition to 931,423. 


932,289—Aug. 24, 1900. P. Jutius and L. Biancry, Germany. (Badische.) 
Azo dye and process of making. 


2.6-DINITRANILIN diazotized preferably in mineral acid soln. using conc. H,SO, and nitrosyl 
sulfate, and coupled after dilution with 2-NAPHTHOL, pptd. with substratum if desired to form 
lake. A RED dye suitable for lakes, fast to aq., alc., lime, light, oil, and heat. 

Near S. 132.—‘‘Lake Red P.” 


932,812—Aug., 21, 1909. F. RunxeL and M. Herzperc, Germany. (Bayer.) 
Disazo dye. 


SULFANILIC acid, freshly pptd., coupled in acid soln. with freshly pptd. 1-AMINO’ 8-NAPHTHOL 
4-sulfo then combined in alk. soln. with diazo 2-amino PHENYL 2/-ToLyri ether. Other com- 
ponents claimed. A BLUE, GREEN or BLACK acid dye, fast to washing and milling. 

Note 932,813. 


933,446—Sept. 7, 1909. L. Hessz, O. GuNTHER, and A. Zart, Germany. (Bayer.) 
Azo dye. 


ANILIN 2-sulfo or other amin with negative group in ortho position, coupled in acetic soln. 
with CRESIDIN or other, rediazotized and coupled with phenyl 1.2-NAPHTHIMIDAZOLE 5-oxy 7-sulfo 
or other. See lists of other components. A RED to BLUE direct dye, fast to light. 

Note 795,869 and 792,600 for thiazol, imidazol and urea compounds, and also 933,447-48 and 
933,562. 


GROUP VI.—AZO 149 


933,447—Sept. 7, 1909. L. Hesszt, O. GuntHER, and A. Zart, Germany. (Bayer.) 
Azo dye. 

I-NAPHTHYLAMIN 2.4-disulfo or other amin with sulfo or nitro group in ortho position, coupled 
in acetic soln. with 4-xyLIDIN, or other, rediazotized and coupled in alk. soln. with phenyl 
2-AMINO 5-NAPHTHOL 7-sulfo or thiazol, imidozol, or other comps. RED, VIOLET or BLUE dyes, fast 
to light. 

Note 795,869, 792,600 and 933,446. 


935,371—Sept. 28, 1909. Paul Jutius and Ernst FussENEGGER, Germany. (Badische.) 
Azo dye. 


Acetyl 2-ToLUIDIN 4-sulfo, treated with chlorine in aq. soln. then saponified to form 6-chlor 
2-TOLUIDIN 4-sulfo which is coupled with 2-NAPHTHOL. ORANGE to YELLOW lakes, fast to light. 


936,321—Oct. 12, 19009. Johannes JANSEN and Wilhelm NEELMEIER, Germany. (Bayer.) 
Azo dye. 


PicrRAMIc acid coupled with 4-chlor PHENOL, or other. Yellow Brown mordant dyes that 
may be dyed by one bath method and are fast to light. 


936,367—Oct. 12, 1909. Arnold ScHEDLER, Switzerland. (Basle.) 
Orange to red tetrazo dye and process of making same. 


3-AzOxY TOLUIDIN derived from 4-nitro 2-toluidin coupled in alk. soln. with 2 mols, 3/- 
amino phenyl PYRAZOLONE carbo, or other. Mixed second components may be used and also as 
first components ethers, thio ethers, stilbenes, ureas, ethylene ether, etc. 


936,456—Oct. 12, 1909. Myrtil Kaun, Germany. (Elberfeld.) 
Azo dye. 


4-Amino CHRYSOIDIN made by coupling acetyl 4-PHENYLENE DIAMIN with 3-PHENYLENE 
DIAMIN and saponifying, coupled with 1-AMINO 8-NAPHTHOL 4.6-disulfo or other, then dyed or 
printed on fiber and coupled in bath of diazo 4-NITRANILIN. Buacx developed dye. 


936,951—Oct. 12, 1909. Otto Scumipt, Germany. (Badische.) 
Azo dye. 


4-PHENYLENE DIAMIN 3-sulfo condensed with BENZoy1, chloride or derivs., to form benzoyl 
4-PHENYLENE DIAMIN 3-Sulfo which is coupled with 2-NAPHTHOL 3.6-disulfo or other. Dyes give 
RED lakes, fast to light. 


938,813—Aug. 31, 1909. F. RunxeL and M. Herzperc, Germany. (Bayer.) 
Azo dye. 


2.5-Dichlor ANILIN coupled in acid soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo then in alk. 
soln. with diazo 2-amino PHENYL ether. Other components claimed. A BLUE, GREEN or BLACK 
acid dye, fast to washing and milling. 

Addition to 932,812. 


933,448—Sept. 7, 1909. L. Hesse, O. GuntTHER and A. Zart, Germany. (Bayer.) 
Azo dye. 


ANILIN 2-sulfo or other amin with sulfo or nitro group in ortho position, coupled in acetic 
soln. with 4-xYLIDIN, rediazotized and coupled in alk. soln. with 2-AMINO 5-NAPHTHOL 1.7- 
disulfo. RrEp to BLUE direct dyes, fast to light. 

Addition to 933,446. 


933,562—Sept. 7, 1909. L. Hesse O. GuNTHER and A. Zart, Germany. (Bayer.) 
Azo dye. 


3-XYLIDIN 6-sulfo or other amin with negative group in ortho position, coupled in acetic 
soln. with 4-xYLIDIN, rediazotized and coupled in alk. soln. with phenyl 2-AMINO 5-NAPHTHOL 7- 
sulfo. Other components claimed. A RED to BLUE direct dye, fast to light. 

Addition to 933,446. 


933,841—Sept. 14, 1909. J. Jansen and W. NEELMEIER, Germany. (Bayer.) 
Azo dye. 


s-Nitro 4-chlor 2-amino PHENOL or other ortho amino phenol with nitro or chlor sub- 
stitutents but no sulfo or carbo group, coupled with 3-oxy dimethyl ANILIN or other, in acetic or 


150 DIGEST OF PATENTS 


alk. soln. Rep to VIOLET or BLACK acid mordant (Cr) dyes that can be dyed by one bath 
method and are fast to light. 
Addition to 924,231. 


933,842—Sept. 14, 1909. J. Jansen and W. NeELMEIER Germany. (Bayer.) 


Azo dye. 


4-Nitro 2-amino PHENOL, or other, coupled in alk. soln. with 2.6-dioxy NAPHTHALENE. Other 
components claimed. A BLACK acid mordant (Cr) dye that can be dyed by one bath method. 
Near S. 159.—‘‘Acid Alizarin Black R.”’ Addition to 924,231. 


935,016—Sept. 28, 1909. O. GuntHER and L. Hessz, Germany. (Bayer.) 
Yellow dye. 


SULFANILIC acid azo 2-ANISIDIN, 2 mols., or other amino azo dye, in dil. soln. mixed with 
PHOSGENE to form urea comp. A YELLOW direct dye, fast to light. 
Note 935,017 and 18. 


925,017—Sept. 28, 1909. O. GuntTueER and LL. Hesse, Germany. (Bayer.) 
Yellow azo dye. 


3-Amino BENZOIC acid azo 2-ANISIDIN, 2 mols., mixed in alk. soln. with one mol. PHOSGENE 
to condense into urea comp. A green-YELLOW direct dye, fast to light. 
Addition to 935,016. 


935,018—Sept. 28, 1909. O. GuntHErR and I. Hessz, Germany. ((Bayer.) 
Azo dye. 


I-NAPHTHYLAMIN 3.6-disulfo azo 4-CRESIDIN, 2 mols., mixed in alk. soln. with one mol. 
PHOSGENE. Other components claimed. YELLOW to ORANGE direct dyes, fast to light. 
Addition to 935,016. 


935,031—Sept. 28, 19009. M. Kaun and A. OssenspEcK, Germany. (Bayer.) 
Azo dye. 


Dinitro 2-amino 3-CRESOL,* coupled in alk. soln. with phenyl 2-AMINO 5-NAPHTHOL 7-sulfo. 
Other components claimed. VIOLET and BLACK acid and developed (CrO,) dyes. 


941,088—Nov. 23, 1909. Carl Oskar MUt.yuer, Germany. (Hdéchst.) 
Azo dye and process of making same. 


4'-Nitro benzoyl 4-PHENYLENE DIAMIN, or meta deriyv., coupled in alk. soln. with acetyl 
2-AMINO 5-NAPHTHOL 7-sulfo, then reduced with Na,S at 60°. Rep direct and developed dyes, 


that can be coupled on fiber and then are fast to washing. 
Near S. 66.—‘‘Amino Naphthol Red 6B.” 


942,916—Dec. 14, 1900. Wilhelm Konic, Germany. 
Red azo dye for lakes and process of making same. 


2-Chlor ANILIN 5-carbo acid, coupled in alk. soln. with 2-oxy 3-NAPHTHOIC acid, m. p. 216°. 
Lakes with Ba, Ca, or Pb. may be pptd. using BaSO, or Al(OH), as substratum. Other com- 
ponents claimed. Rep lakes fast to light, aq., alc. and oil. 


943,470—Dec. 14, 1909. Arnold ScuHepLer, Switzerland. (Basle.) 
Red disazo dye and process of making same. 


4-XYLIDIN coupled in alk. soln with 3’-amino phenyl 1.2.-NAPHTHIMIDAZOLE 5-oxy 7-sulfo, re- 
diazotized and coupled in alk. soln. with 3’-amino 1-phenyl PYRAZOLONE carbo. Rep direct dyes 
that can be coupled on fiber and are then fast to acids and washing. 


943,536—Dec. 14, 1909. Huco GrLpERMANN, Germany. (Berlin.) 
Mordant-dyeing azo dye. 


2-Chlor 4-NITRANILIN coupled in carbonate soln. with saLicytic acid or 2-or 4-CRESOTINIC 
acid. ORANGE to RED acid and acid mordant (Cr) dyes, which when chromed are fast to acids, 
alk. and light. 


* For preparation of cresol comp., see Ann. der Chem., 163, 104 


'* 
ee ere 


GROUP VI.—AZO I51 


944,328—Dec. 28, 1909. Carl HemeEnreicu, Germany. (Bayer.) 
Disazo dye. 
4-NITRANILIN 2-sulfo, coupled in alk. soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo, then com- 


bined in weak acid soln. with diazo 4-NITRANILIN 2-sulfo, and finally in alk. soln. with diazo 
ANILIN. Other components claimed. Butacx acid dyes, fast to light. 


945,780—Jan. 11, 1910. Oscar GunTHER and Leopold Hessz, Germany. (Bayer.) 
Black azo dye. 
5-Nitro 2-ANISIDIN or other, coupled with phenyl 2-amino 8-NaPHTHOL 6-sulfo or other, 


Buack acid dyes. 
Near S. 99.—‘‘Tuscalin Orange G.’”’ 


946,050—Jan. 11, 1910. Myrtil Kaun, Germany. (Bayer.) 
Brown dye. 

3-Diamino DIPHENYL urea coupled in alk. soln. with 1 mol. each of 3-PHENYLENE DIAMIN 4- 
sulfo acid and 3-PHENYLENE DIAMIN, or other. Other components claimed. Brown direct and 
developed (coupled) dyes, that can be developed on fiber with diazo salts, and are then fast 
to washing, and discharge pure white. 

Note 946,051 and 52. 


946,051—Jan. 11, 1910. Myrtil Kaun, Germany, (Bayer.) 
Brown dye. 


Diamino pDIPHENYL urea coupled in alk. soln. with 1 mol. each of (4) 3-TOLUYLENE DIAMIN 6- 
sulfo and 3-PHENYLENE DIAMIN, or other. Brown direct and developed (coupled) dyes which 
when developed on fiber with diazo 4-nitranilin are fast to washing and give pure white dis- 
charge. 

Addition to 946,050. 


946,052—Jan. 11, 1910. Myrtil Kaun, Germany. (Bayer.) 
Brown coloring-matter. 


Diamino DIPHENYL urea coupled in alk. soln. with 1 mol. each of 3-amino PHENOL 6-sulfo 
or other, and RESORCIN, or other. Brown direct and developed (coupled) dyes that can be de- 
veloped on fiber with diazo 4-nitranilin and then are fast to washing and give pure white dis- 
charge. 

Addition to 946,050. 


949,633—Feb. 15, rg10. Heinrich Oster, Germany. (Berlin.) 
Azo dye for chromed wool and process of making same. 


2.5-Dichlor ANILIN 4-sulfo, coupled with saticyLic acid, or other. ORANGE to RED acid and 
developed (CrO,) dyes, fast to light. 


950,404—Feb, 22, 1910. Friedrich RuNKEL and Martin Herzperc, Germany. (Bayer.) 
Azo dye. 


4-Chlor 2-amino PHENYL ether, homologs or derivs., diazotized while hot, nearly neutralized 
and coupled in weak acid soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo or derivs., then combined 
with diazo 3-NITRANILIN, etc. GREEN to BLUE to BLACK direct dyes, fast to washing and milling. 
Note 932,812 and 173. 


950,405—Feb. 22, 1910. Friedrich RuNKEL and Martin Herzprerc, Germany. (Bayer.) 
Azo dye. 


2.5-Dichlor ANILIN coupled with 1 mol. each of 1-AMINO 8-NAPHTHOL 3.6-disulfo and 2-amino 
4-chlor DIPHENYL ether. Blue siacx acid dye, fast to washing and milling. 
Addition to 959,404. 


953,033—Mar. 29, 1910. Martin Herzperc and Friedrich RuNKEL, Germany. (Bayer.) 
Brown azo dye. 


Sulfo acid of 2-amino 4’-chlor pIPHENYL ether or other, coupled with phenyl 2-aAmMINo 8- 
NAPHTHOL 6-sulfo or other. Brown acid dye, fast to washing and milling. 
Addition to 950,404. 


152 DIGEST OF PATENTS 


953,034—Mar. 209, 1910. Martin Herzperc and Friedrich RunxeL, Germany. (Bayer.) 
Azo dye. 


2-Amino 4/-chlor pIPHENYL ether or other, coupled with phenyl 2-AMINo 8-NAPHTHOL 6-sulfo 
or other. Brown acid dyes fast to milling and washing. 
Addition to 950,404. 


953,035—Mar. 29, 1910. Martin Herzserc and Friedrich RunxeL, Germany. (Bayer.) 
Brown azo dye. ie 
Same as 953,033, being specific claims of which the latter patent covers general claims. 


Brown acid dye. 
Addition to 950,404. 


954,960—Apr. 12, 1910. Wilhelm Herzperc and Max Ronus, Germany. (Berlin..) 
Red azo dye and process of making same. 


5-Nitro 2-TOLUIDIN coupled with 2-NAPHTHOL. Lakes are formed in usual way with sub- 
stratum such as Al(OH), etc. Rep lakes, fast to light, alc., aq. and oil. 
Note 955,068. 


955,068—Apr. 12, 1910. Wilhelm Herzperc and Max Ronus, Germany. (Berlin.) 
Azo dye and process of making same. (Process not claimed.) 

3-Chlor 5-nitro 2-ToLUIDIN or other halogen deriv., coupled with 2-NAPHTHOL. RED lakes, fast 
to light, aq., ale., and oil. 

Addition to 954,969. Same as patent 954,960 with halogen added to first component. 
958,774—May 24, I910. Franz Scuoit, Germany. (Hdchst.) 
Black mono-azo dye and process of making. 


4-Chlor 2-amino PHENOL coupled with 1-AMINO 8-NAPHTHOL 5-sulfo, with or without milk 
of lime, to neut. coupling soln. Blue BLack acid mordant dyes, fast to light, hot pressing, 
milling, potting and acid boiling. 


958,830—May 24, 1910. Friedrich RunKEL and Martin Herzperc, Germany. (Bayer.) 
Dye. 

3-Amino DIPHENYL ether, or other, sulfonated in conc. H,SO, then coupled with 1-amiINo 8- 
NAPHTHOL 4-sulfo, or other, and combined with diazo 4-chlor 2-amino DIPHENYL ether or other. 
BLUE to GREEN to BLACK acid dyes, fast to washing and milling. 

Addition to 950,406. 


958,912—May 24, 1910. Karl Exvset, Germany. (Kalle.) 
Nitro-ortho-oxy-azo colors and process of making same. 


I-AMINO 2-NAPHTHOL 4-sulfo, or other, diazotized, zinc salt formed, then nitrated, Zn salt 
pptd., and finally coupled with 1-NAPHTHOL, or other. Blue Gray to BLACK acid and acid mor- 
dant dyes, fast to potting and will not stain cotton in acid dye bath. 


959,07 8—May 24, 1910. Karl ScunitzspauHn, Germany. (Griesheim.) 
Orange azo dye. (Process also claimed.) 


4-Chlor ANILIN, or other, coupled with 2-NAPHTHYLAMIN 3.6-disulfo. ORANGE acid dyes, suit- 
able for lakes, those with two or three chlorine atoms or with one or two chlorine atoms and 
one sulfo group are especially fast to acids and light. 


959,109—May 24, 1910. Melchior BonicEr, Switzerland. (Sandoz.) 
Orange disazo dye and process of making. 


To.ipIn, coupled with 1 mol. each of saticyLic acid and 4’-sulfo phenyl methyl PYRAZOLONE. - 
Other components claimed. ORANGE direct dye, fast to acids, alkalies, and light. 


961,254—June 14, 1910. Johannes JansEN and Wilhelm NEELMEIER, Germany. (Bayer.) 
Green azo dye. 

Azo dye in which peri diamino component is converted into azimino deriv. 6-Chlor 4-nitro 
2-amino PHENOL or other, coupled with 1.8-NAPHTHALENE DIAMIN 4-sulfo, then treated in acid 
soln. with nitrous acid at low temp. to form azimino comp. Yellow GREEN and VIOLET acid and 
acid mordant dyes. 


GROUP VI.—AZO 153 


961,355—June 14, 1910. Johannes Jansen and Wilhelm Nerumeier, Germany. (Bayer.) 
Red azo dye. 


2-Amino I-PHENOL 4-sulfo, or other, coupled with 6.8-dioxy QguiNoLIN. YELLOW to RED acid 
and acid mordant dyes, fast to light and fulling. 


963,739—July 12, 1910. Wilhelm Brrcpout, Germany. (Bayer.) 
Azo dye. 
4-PHENYLENE DIAMIN Coupled with 2-AMINO 8-NAPHTHOL 6-sulfo, tetrazotized and coupled with 


1 mol. each of 3-PHENYLENE DIAMIN 4-sulfo and phenyl 2-AMINO 5-NAPHTHOL 7-sulfo. Other 
components claimed. Blue BLack direct dyes. 


964,786—July 19, 1910. Myrtil Kaun and Anton OssensBecK, Germany. (Bayer) 
Azo dye. 


3-Amino BENzoIc acid, or other, coupled with acetyl 1-amMINo 8-NAPTHOL 3.6-disulfo or 
other. Rep acid mordant (Cr) dyes suitable for printing. 


964,918—July 19, 1910. August Leopold Lasxa, Germany. (Griesheim.) 
Bluish-red disazo dye. (Process also claimed.) 


2.2’-Dichlor DIANISIDIN coupled with 2 mols. 2-NAPHTHOL. Presence of Turkey Red oil or 
soap is recommended. Blue rEp dye, suitable for lakes. Note 964,920, 971,761 and 62. 


964,919—July 19, 1910. August Leopold Lasxa, Germany. (Griesheim.) 
Brown mordant azo dye. (Process also claimed.) 


2-Amino PHENOL 4-sulfo or other, coupled with 4-nitro 3-PHENYLENE DIAMIN or other. 
Red Brown acid and developed (CrO,) dyes, fast to light. 


964,920—July 19, 1910. August Leopold Lasxka, Germany. (Griesheim.) 
Disazo dye. (Process also claimed.) 
2.2'-Dichlor DIANISIDIN, coupled with 2 mols. 2-NAPHTHOL 3.6-disulfo. Other components 


claimed. VuioLetr to RED fast dyes, suitable for lakes. 
Addition to 964,918. 


965,882—Aug. 2, 1910. 
Oscar DreEssEL, Richard Koruet, and Heinrich Horrntern, Germany. (Bayer.) 
Azo dye. 
4-TOLUIDIN 2-sulfonanilid, coupled with 4’-sulfo phenyl methyl pyrazoLong. Other components 
claimed. YELLOw acid dyes, fast to fulling and washing. 


969,450—Sept. 6, 1910. August BLANK and Karl Heusner, Germany. (Bayer.) 
Azo dye. 

4-Amino ACETANILID, coupled in alk. soln. with 2-AMINO 5-NAPHTHOL 7-sulfo, saponified by 
boiling in dil. NaOH soln. then tetrazotized and coupled with 1 mol. each of 1-AMINO 8-NAPHTHOL 
4.6-disulfo and rEsorcIN. Other components claimed. BuLugr and siacKk direct and developed 
(coupled) dyes, fast to light, that can be diazotized on fiber and discharged pure white. 

Note 971,111, and 971,112. 


971,111—Sept. 27, 1910. August BLank and Wilhelm Brrcpo.it, Germany. (Bayer.) 
Trisazo dye. 

Formyl 3-PHENYLENE DIAMIN, coupled in alk. soln. with 2-AMINO 8-NAPHTHOL 6-sulfo, then 
saponified by boiling in dil alk., tetrazotized and coupled with 2 mols. 3-TOLUYENE DIAMIN. Other 
components claimed. Brown direct and developed dyes, fast to acids, and when developed by 
diazo 4-nitranilin are fast to washing. 

Note 960,450 and 971,112. 


971,112—Sept. 27, 1910. August BLanx and Wilhelm Brrcpoit, Germany. (Bayer.) 
Trisazo dye. 

Formyl 3-PHENYLENE DIAMIN coupled with 2-AMINO 8-NAPHTHOL 6-sulfo, saponified, tetra- 
zotized and coupled with 3-PHENYLENE DIAMIN. and 3-PHENYLENE DIAMIN glycin. Brown direct 
and developed (coupled) dye, fast to acids and fast to washing when developed by diazo 4- 
nitranilin. 

Addition to 971,111. 


154 DIGEST OF PATENTS 


971,761—0Oct. 4, 1910. August Leopold Lasxa, Germany. (Griesheim.) 
Yellow disazo dyestuff for wool. (Process also claimed.) 

3-TOLIDIN 3.3’-dichlor benzidin or other, coupled with 2 mols. 4’-sulfo phenyl methyl 
PYRAZOLONE or other. YELLOW direct dyes, suitable for lakes, fast to white wool and cotton 
in milling process, without after treatment with chromates. 

Addition to 964,918. 
971,762—Oct. 4, 1910. August Leopold Lasxa, Germany. (Griesheim.) 
Yellow azo dyestuff for wool. (Process also claimed.) 

3-TOLIDIN or 3.3/-dichlor benzidin, etc., coupled with 1 mol. each of saLicyLic acid and 4’- 
sulfo phenyl methyl PyRAzoLONE. Other components claimed. YELLOW direct dyes, fast in mill- 
ing process. 

Addition to 964,918. 


974,346—Nov. 1, 1910. Wilhelm Brrcpo.tt, Germany. (Bayer.) 
Green azo dye. 
TOLIDIN or other para diamin tetrazotized and combined with 1 mol. each of SALIcyLic acid 


or other ortho oxy carbo acid and ANnILIN disulfo azo 1-amino 8-NAPHTHOL cas -sulfo. GREEN direct 
dyes, especially suited for dyeing half-wool. 


976,401—Nov. 22, 1910. Karl ScHNITZSPAHN, Germany. (Griesheim.) 
Monoazo dye for lakes. (Process also claimed.) 


2-NAPHTHYLAMIN 4.8-disulfo coupled with 2-oxy 3-NAPHTHOIC acid. Blue rep lakes, fast to oil 
and light. 


978,438—Dec. 13, 1910. 


Oscar DressEL, Richard Korue and Heinrich Horrtern, Germany. (Bayer.) 
Dye. 
4-Toluidin 1-NAPHTHYL 2-sulfonamid 5-sulfo acid, coupled with 2-methyl INDOLE or other. 
Green YELLOW acid dyes, fast to milling, washing and light. 
Note 978,439. 


978,439—Dec. 13, 1910. 
Oscar DreEssEL, Richerd KotHE and Heinrich HorritErn, Germany. (Bayer.) 
Dyestuff. 
ToLvuipIn sulfon anilid, or other, coupled with 2-methyl INDOLE sulfo. YELLOW acid dye, fast 
to light and milling. 
Addition to 978,438. 


978,580—Dec. 13, 1910. 
Oscar GuNTHER, Leopold Hrssg and Arthur Zart, Germany. (Bayer.) 
Dye. 
Ureas of sulfo acids of amino diazo compounds. 
SULFANILIc acid coupled with ANILIN 2-sulfo, rediazotized and coupled with crEsIDIN, then 
in alk. soln. condensed with PHOSGENE to an urea. Other components claimed. RzEp and YELLOW 
to BROWN direct dyes, fast to light. 


978,865—Dec. 20, 1910. Otto Ernst and Heinrich E1chwepr, Germany. (Hichst.) 
Monoazo dye and process of making same, 


2.4-DINITRANILIN 6-sulfo coupled with 2-oxy 5-NAPHTHOIC acid. Blue RED lakes, suitable for 
wall paper, printing and oil colors, that cover well and are fast to oil and light. 


980,251—Jan. 3, 1911. Arthur HausporFrer and Carl HeipenreIcH, Germany. (Bayer.) 
Azo triphenylmethane dye. 


2-Chlor 3-amino BENZALDEHYDE or other, condensed with 2 mols. 2-cRESOTINIC acid or other, 
then diazotized and combined with a third mol. of 2-cresotinic acid, or other. The diazo com- 
ponent may be different from the condensation components. BROWN, YELLOW and GREEN, OF VARI- 
colored acid and developed (CrO,) dyes, nee when chromed are fast to fulling, potting and 
light. 

Near S. 552.—‘‘Chromate Blue G. for Printing.’? Note 980,521, 1,021,364, 1,021,365 and 
1,021,366. 


GROUP VI:——AZO 155 


980,521—Jan. 3, 1911. Arthur HausporFer and Carl Hripenrreicu, Germany. (Bayer.) 
Azo triphenylmethane dye. 

2-Chlor 3-amino BENZALDEHYDE condensed with 2 mols. 2-CRESOTINIC acid, dissolved in alk. 
carb. and re-pptd., by HCl, separated, diazotized, and coupled in alk. soln. with phenyl methyl 
PYRAZOLONE. YELLOW and GREEN acid and developed (CrO,) dyes, fast to fulling, potting and 
light. 

Note 980,251. 


981,276—Jan. 10, 1911. Johannes Jansen and Wilhelm NEELMEIER, Germany. (Bayer.) 
Azo dye. 
6-Chlor 4-nitro 2-amino PHENOL or other, coupled with 2.4-diamino DIPHENYL ether 4’-carbo. 


acid or other. Yellow srown acid mordant dyes, fast to fulling and light, suitable for one-bath 
mordant dyeing. 


982,507—Jan. 24, 1911. August Leopold Lasxa, Germany. (Griesheim.) 
Disazo dyestufi. (Process also claimed.) 

2.6-TOLUYLENE DIAMIN 4-sulfo with 2 mols. 2-AMINO 5-NAPHTHOL 7-sulfo, in acid soln. 
ORANGE and rEp direct and developed (coupled) dyes, which when coupled with diazo 4-nitranilin 
are fast to washing and give white discharge. 

Note 982,508. 


982,508—Jan. 24, 1911. August Leopold Lasxa, Germany. (Griesheim.) 
Disazo dyestuff. (Process also claimed.) 

2.6-TOLUYLENE DIAMIN 4-sulfo coupled with 1 mol. each of 2-AMINO 8-NAPHTHOL 6-sulfo and 
3-PHENYLENE DIAMIN or other. RED and Brown direct and developed (coupled) dyes, that can 


be coupled on fiber with diazo 4-nitranilin and discharge pure white. 
Addition to 982,507. 


982,509—Jan. 24, 1911. August Leopold Laska, Germany. (Griesheim.) 
Disazo dyestuff. (Process also claimed.) 


2.2'-Dichlor 5.5’-dinitro BENZIDIN obtained by nitration of dichlor benzidin, coupled with 2 
mols. 2-NAPHTHOL. REp lakes, insol. in oil. 


982,952—Jan. 31, IgIt. Oscar GUNTHER and Leopold Hrssz, Germany. (Bayer.) 
Azo dye. i 


4-Nitro 2-ANISIDIN coupled with phenyl 2-AMINO 8-NAPHTHOL 6-sulfo. Other components 
claimed. RED, BROWN to BLACK acid dyes, fast to light and milling. 
Near S. 98.—Naphthol Rose. Note 982,953. 


982,953—Jan. 31, 1911. Oscar GuNTHER and Leopold Hesst, Germany. (Bayer.) 
Azo dye. 


2.4 DINITRANILIN, or other unsulfonated amin, coupled with phenyl 2-AMINO 8-NAPHTHOL 6- 
sulfo or other. Biacxk to RED acid dyes, fast to milling and light. 
Addition to 982,952. 


982,954—Jan. 31, 1911. Oscar GUNTHER and Leopold Hrssz, Germany. (Bayer.) 


Azo dyestuff. 
2-Chlor ANILIN or other, containing no nitro groups, coupled with 4’-anisidyl 2-AMINO 8- 


NAPHTHOL 6-sulfo. RED to vioLET acid and developed dyes, fast to milling and light, that can 
be after chromed to increase fastness. 


982,955—Jan. 31, 1911. Arthur GunTHER and Leopold Hesst, Germany. (Bayer.) 
Azo dye. 


Meraniuic acid or other, coupled with 3-xylyl 2-amMino 8-NaPHTHOL 6-sulfo or other. RED 
to vIoLET acid and developed (CrO,) dyes, fast to milling and light, faster when after chromed. 


983,132—Jan. 31, 1911. Hugo GELDERMANN and Heinrich OstEr, Germany. (Berlin.) 
Monoazo dyestuff for chrome-mordanted wool. 


Acetyl 4.2-diamino PHENOL 6-sulfo, coupled with phenyl methyl pyrazoLonEe. Rep acid mor- 
dant (Cr) dyes, fast to light. 
II 


156 DIGEST OF PATENTS 


983,486—Feb. 7, 1911. Otto Ernst and Heinrich E1cuwepe, Germany. (Hdéchst.) 
Monoazo dyestuff and process of making same. 


6-Chlor 3-ro.umpin 4-sulfo coupled with 2-oxy 3-NAPHTHOIC acid. Rep lakes, fast to light. 
Near S. 153—‘‘Lake Red C.” Addition to 733,280. 


983,805—Feb. 7, 1911. Erich Bertuoip, Germany. (Berlin.) 
Monoazo dye. 


4-Amino DIPHENYLAMIN coupled with rEsorcIN. Brown lakes for lithography, wall paper, 
varnishes, wood stains, etc. 


984,900—Feb. 21, 1911. Hugo GELDERMANN, Germany. (Berlin.) 
Monoazo dyestufif and process of making same. (Process not claimed.) 
4-Chlor ANILIN 3-sulfo coupled with phenyl methyl pyrazoLonr. YELLOW acid dye, fast to 


light. 
Near S. 22.—‘‘Xylene Yellow.”’ 


986,287—Mar. 7, 1911. Wilhelm Hrrzperc and Oswald ScHarFEnBERG, Germany. (Berlin.) 
Monoazo dye for wool. 


4-Nitro 2-amino PHENOL 6-sulfo condensed with PHOSGENE to an urea which is tetrazotized 
and coupled with 2 mols. 2-Naphthol. Brown-rep to dark vioLetT acid and acid mordant (Cr) 
dyes. 


987,362—Mar. 21, 1911. Wilhelm Herzperc, Germany. (Berlin.) 
Monoazo dyes for wool. 


PicraAmic acid coupled with 5-amino 2-CRESOL, ethyl ether, 3-ethoxy 4-TOLUIDIN, or other meta 
amino phenol ether or halogen deriv. thereof. Green BRowNn acid mordant (Cr. one bath) dyes, 
fast to milling, potting and light. 

Near S. 90.—‘*Chrome Brown.” 


987,417—Mar. 21, 1911. Joseph Turner and Harry Dean. (England.) 
Direct-dyeing cotton dyestuff. 


2-or 4-Chlor ANILIN coupled in weak acid soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo ‘‘H,”’ 
product combined in alk. soln. with one equivalent of tetrazo BENZIDIN which is then coupled with 
3-PHENYLENE DIAMIN, (or para). Brack direct dyes. 

Note 1014982 and 83. 


987,999—Mar. 28, rort. August Leopold Lasxka, Germany. (Griesheim.) 
Process of making ortho-oxymonoazo dye. (Product also claimed.) 


4-Nitro 6-amino SALIcyLic acid, coupled with 4-crEsoL. YELLOW to BROWN acid and de- 
veloped (CrO,) dyes, which when after chromed are fast to milling, potting and light. 


988,000—Mar. 28, tg11. August Leopold Lasxa, Germany. (Griesheim.) 


Substantive diazo dyestuff. (Process also claimed.) 


3.3’-Dichlor BENZIDIN, coupled with 1 mol. each of 1-AMINO 8-NAPHTHOL 3.6-disulfo and 


nitro 3-PHENYLENE DIAMIN. Other components claimed. Brown and brown GREEN direct and de- 
veloped (coupled) dyes, which when coupled with diazo 4-nitranilin are fast to soap and of 
good covering power. ’ 


989,000—Apr. 11, I91I Oscar GUNTHER and Leopold Hesse, Germany. (Bayer.) 


Azo dyestuff. 

2.4-DINITRANILIN coupled in acid soln. with 2-AMINO 8-NAPHTHOL 6-sulfo. Blue BLACK 
acid dye, fast to fulling, light and boiling mineral acids. 

Note 989,001. 


989,001—Apr. 11, IgII. Arthur GuntHER and Leopold Hessz, Germany. (Bayer.) 
Azo dyestuff. 

2.4-DINITRANILIN coupled in acid soln. with phenyl 2-NAPHTHYLAMIN 6-sulfo, or other. BLAcK 
or BRown acid dyes, fast to fulling, light and mineral acids. 

Addition to 989,000. 


GROUP VI.—AZO 157 


989,953—Apr. 18, 1911. 
Oscar DressEL, Richard Korue, and Alfred Tuauss, Germany. (Bayer.) 
Dye. 
2-TOLUIDIN or other, coupled with 3’-amino phenyl 5-oxy 7-sulfo 1.2-NAPHTHIAZOLE, re-diazo- 
tized and coupled with NAPHTHIONIC acid, or other. Rep direct dyes, fast to mineral acids. 


989,954—Apr. 18, 1911. 
Oscar DressEL, Richard Korue and Heinrich Horrie1n, Germany. (Bayer.) 
Dye. 
4-TOLUIDIN 2-sulfon anilid or other, coupled with 2-NaAPHTHOL 6-sulfo. ORANGE to RED acid 
dyes, fast to milling, washing and light. 


990,173—Apr. 18, 1911. 
7 Victor ViLLIcER and Ernst FussEnrccER, Germany. (Badische.) 
Yellow azo dyes. 


4-Chlor 2-NITRANILIN or other, coupled with aceto ACETANILID or other. YELLOW lakes, fast 
to water, oil and light. 


991,750—May 9, 10911. Bernhard Ricuarp, Switzerland. (Geigy.) 
Mordant-dyeing azo dyes and process of making same. : 


4-NITRANILIN 2-sulfo, coupled with saLicyLic acid, or other. Orange YELLOW to red ORANGE 
acid and developed (CrO,) dyes, which when chromed are fast to milling and potting. 
S. 135—‘‘Eriochrome Phosphin R.” 


993,020—May 23, 1911. Karl Brenzincer, Germany. (Bayer.) 
Azo dye. 


Benzyl azimino 2-ToLuIDIN coupled with phenyl 2-AMINO 8-NAPHTHOL 6-sulfo. Brown acid 
and developed (CrO,) dye, which after chroming is fast to milling. 


993,073—May 23, I911. Heinrich Jorpan and Wilhelm NEELMEIER, Germany. (Bayer.) 


Azo dye. 


ANILIN or other, coupled with 3”-amino benzoyl 3’-amino benzoyl 2-AMINO 5-NAPHTHOL 7- 
sulfo. ORANGE direct and developed (coupled) dyes, that can be diazotized on fiber and coupled 
with naphthol, etc. 


993,549—May 30, rort. Bernhard Ricuarp, Switzerland. (Geigy.) 
Azo dye and process of making same. 


3-NITRANILIN 4-sulfo acid, coupled with 3-amino 4-CRESOL, in presence of thiosulfate, etc., 
again diazotized and coupled with 2-NaPHTHOL. Other components claimed. ORANGE, RED and 
blue-crEEN acid and developed (CrO,) dyes, which when chromed are fast to potting, milling and 
light. 


995,160—June 13, 1911. August Leopold Lasxa, Germany. (Griesheim.) 
Orange cotton dyes. (Process also claimed.) 


BENZIDIN 2-sulfo, coupled with 1 mol. each of 4’-sulfo phenyl methyl pyRAzoOLONE and nitro 
3-PHENYLENE DIAMIN. Other components claimed. ORANGE to orange RED direct dyes, fast to 
acids and light. 


995,161—June 13, 1911. August Leopold Lasxa, Germany. (Griesheim.) 
Disazo dyes for wool. (Process also claimed.) 


4-TOLIDIN, or 3.3/-dichlor tolidin, coupled with 1 mol. each of saLicyzic acid and phenyl 2- 
AMINO 8-NAPHTHOL, 6-sulfo. Other components claimed. Yellow Brown acid dyes that will not 
stain white wool or cotton in milling process. 


997,061—July 4, 1911. Wilhelm Herzperc and Werner Lancrt, Germany. (Berlin.) 
Tetrakisazo dye. 


METANILIc acid coupled in acid soln. with sym. -3.3’-diamino DIPHENYL trea, tetrazotized and 
coupled with 2 mols. 3-PHENYLENE DIAMIN in alk. soln. Brown direct and developed (coupled) 
dyes, which when developed with diazo -4-nitranilin are deeper brown, and fast to washing and 
light. 


158 DIGEST OF PATENTS 


999,230—Aug. 1, 1911. Georg Katiscuer, New York. (Cassella.) 
Azo dye. (Process also claimed.) 

ANILIN coupled with 3/-amino phenyl 3-oxy 6-sulfo 1.2-NAPHTHIMIDAZOLE, obtained by con- 
densing amino BENZALDEHYDE bisulfite with 1.2-DIAMINO 3-NAPHTHOL 6-sulfo. Products may be 


diazotized and coupled with 2-NAPHTHOL 6-sulfo. YELLOW to RED direct and developed (coupled) 
dyes, which when coupled on fiber are fast to washing. 


999,558—Aug. 1, 1911. Rudolf Haucwitz, Germany. (Berlin.) 
Polyazo dye and process of making same. (Process not claimed.) 
4-PHENYLENE DIAMIN aZO CRESIDIN tetrazotized and coupled in alk. soln. with 1 mol. each of 


I-AMINO 8-NAPHTHOL 2.4-disulfo and 3-PHENYLENE DIAMIN. Other components claimed. Bius and 
BLACK direct and acid mordant dyes. 


999,713—Aug. 1, 1911. Herbert Gorxe, Germany. (Bayer.) 
Brown basic azo dye. 

4-Amino benzyl DIMETHYLAMIN coupled with 2-amino BENZIDIN, tetrazotized and coupled- 
with two mols. 3-TOLYLENE DIAMIN. Or an acetylated diamino compound may be used as first 
component, the resulting intermediate hexazotized and coupled with 3 mols. of third component. 
Other components claimed. Brown to sLack direct dye for artificial silk (Chardonnet,) fast to 
aq. 


999,797—Aug. 8, tog11. Heinrich Jorpan, Germany. (Bayer.) 
Reddish-blue trisazo dye. 


Oxalyl 4-PHENYLENE DIAMIN coupled in acetic soln. with 1-NAPHTHYLAMIN 6-sulfo, rediazo- 
tized and coupled with a second mol. of 1-NAPHTHYLAMIN 6-sulfo, further diazotized and coupled 
with phenyl methyl pyRAZOLONE.. Other components claimed. VioLeT to BLUE direct and de- 


veloped (coupled) dyes, that can be coupled on fiber and then are fast to washing and light, 
and give white discharge. 


999,944—Aug. 8, 1911. Arthur Zart and Hugo Scuwe1tzER, Germany. (Bayer.) 
Yellow disazo dye. 


Urea of azo compound from 3-phenylene diamin sulfo and cresidin. Formyl 3-PHENYLENE 
DIAMIN 4-sulfo coupled with crEsIDIN then condensed in alk. soln. with PHOSGENE to an urea and 
boiled in dil. alk. to saponify formyl radicals. Other components claimed. YELLOW to ORANGE 
direct and developed (coupled) dyes, that combine with diazo 4-nitranilin on fiber, and then are 
fast to washing. 


1,000,269—Aug. 8, 1911. Heinrich Jorpan and Wilhelm NEELMEIER, Germany. (Bayer.) 
Blue disazo dye. 


s-Amino 4-chlor acetyl] ANISIDIN coupled with 1-NAPHTHYLAMIN 6-sulfo in acetic soln., re- 
diazotized and coupled in alk. soln. with 1-NAPHTHOL 3-sulfo, then saponified. Buiug direct and 


developed (coupled) dyes, that can be coupled on fiber and then are fast to washing and light, 
and can be discharged white. 
Note 1,010,433. 


1,000,606—Aug. 15, 1911. Martin Kaun and Anton OssENBECK, Germany. (Bayer.) 
Black trisazo dye. 


Acetyl 4-PHENYLENE DIAMIN coupled in alk. soln. with 2-AMINO 8-NAPHTHOL ‘6-sulfo, saponi- 
fied, tetrazotized and coupled in alk. soln. with : mol. each of 1.8-NAPHTHALENE DIAMIN 4-sulfo., 
and 2.6-fTOLUYLENE DIAMIN. Other components claimed. Brack direct and developed (coupled) 
dyes that can be developed by diazo 4-nitranilin then are fast to light and washing. 

Near S. 436—‘‘Columbia Black PB.” 


1,001,183—Aug. 22, 1911. Arthur Zart and Hugo ScHwei?TzEeR, Germany. (Bayer.) 
Yellow disazo dye. 

Formyl 3.5-diamino BENzoIc acid, coupled with crEsIpDIN then in carb. soln. condensed with 
PHOSGENE to an urea. Other components claimed. YELLOW to ORANGE direct and developed 
(coupled) dyes, which when developed on fiber with diazo 4-nitranilin are fast to washing. 


GROUP VI.—AZO 159 


1,001,458—Aug. 22, 1911. Karl Scuirmacuer and Richard Leorotp, Germany. (Hdéchst.) 
Bluish-red azo dyestuff. 


5-Nitro 2-amino BENZYL sulfo coupled with 2-oxy 3-NAPHTHOIC acid. Rep dye, suitable for 
lakes, fast to light. 


1,002,286—Aug. 22, 1911. August Leopold Lasxa, Germany. (Griesheim.) 
Disazo dyes and process of making same. 


_2.2'-Dichlor BENzIDIN, coupled in acid soln. with 2 mols. phenyl methyl pyrazoLonE. YELLOW 
to RED lakes, fast to aq. and oil. 


1,003,293—Sep. 12, 1911. Heinrich Porrxier, Germany. (Berlin.) 
Monoazo dye. 


4-Chlor 2-amino PHENOL 6-sulfo coupled with 2-NAPHTHOL 3-carbo acid. VioLer acid and 
developed (CrO,) dyes and lakes. 


1,003,293—Sept. 11, 1911. Heinrich Poiikier, Germany. (Berlin.) 
Monoazo dye for wool. 


2.5-Dichlor ANILIN coupled with ethyl benzyl anizin sulfo. YELLow acid dye, fast to 
washing. 


1,005,235—Oct. 10, 1911. 
Richard Korner, Oscar DresseL and Heinrich HoreryEin, Germany. (Bayer.) 
Orange wool-dye. 


2-TOLUIDIN 5-sulfone 2’-anisidid coupled in alk. soln. with acetyl 2-AMINO 5-NAPHTHOL 7- 
sulfo. ORANGE acid dye, fast to milling and light. 


1,006,051—Oct. 17, 1011. August Buank and Matthias Larten, Germany. (Bayer.) 
Diazotizable green azo dye. 


4-NITRANILIN coupled in acid soln. with 1-AMINO 8-NAPHTHOL 4.6-disulfo or other, reduced 
to amino comp. by Na,S, then condensed in carb. soln. with PHOosGENE to an urea. Mixed azo 
components, etc., also claimed. -GreEN developed dyes, fast to light and washing, oa dis- 
charged and may be developed on fiber with diazo 4-nitranilin. 


1,006,929—Oct. 24, 1911. Hans FrEIMANN, Germany. (Jager.) 
Azo dye. (Process also claimed.) 


2-Amino 3-NAPHTHOL 7-sulfo, two mols. condensed with (2) 3-TOLUYLENE DIAMIN 5-sulfo, by 


means of PHOSGENE to a di-urea product, which is combined in alk. soln with 2 mols. diazo 2- 
TOLUIDIN or other. RED to ORANGE direct dyes, fast to acids. 


1,008,907—Nov. 14, I9II. 
Wilhelm Herzperc, Max Ronus and Franz Scuwaset, Germany. (Berlin.) 
Monoazo dye. 
4-NITRANILIN 2-sulfo coupled with 1.3-diamino 2-chlor BENZENE 5-sulfo or other. Rep acid 
dye, fast to acid, steaming and light. 


1,009,740—WNoyvy. 28, to1t. Oscar GUNTHER, Germany. (Bayer) 
Bluish-red azo dye. 

4.4'-Diamino DIPHENYL urea 3.3’-disulfo coupled with 2 mols. methyl 2-NAPHTHYLAMIN 7- 
sulfo or other. Blue rep direct dyes, fast to light. 

Note 1,009,741. 


1,009,741—Nov. 28, 1911. Oscar GuNTHER, Germany. (Bayer.) 
Red-violet coloring matter. 


4.4/Diamino DIPHENYL urea 3.3-disulfo coupled with 1 mol. each of 2-amino 8-NAPHTHOL 
6-sulfo and phenyl 2-amMiNo 5-NAPHTHOL 7-sulfo. Red vioLer direct dyes, fast to light and iron- 
ing. 

Addition to 1,009,740. 
1,009,745—Nov. 28, 1911. Carl Hemenreicu, Germany. (Bayer.) 
Diazotizable dye. 


BENZIDIN or other para diamin, is coupled with saLicyLic acid then in acid soln. with 1.8- 
AMINO NAPHTHOL 4-sulfo, the diazo comp. of 4-PHENYLENE DIAMIN oxaminic acid is added, soln.. 


160 DIGEST OF PATENTS 


made alk. with Na,CO,, dye separated and saponified in alk.. GrEEN to brown-GREEN direct 
dyes, that may be diazotized on the fiber and developed with 2-naphthol, etc. 


1,009,796—Nov. 28, 1911. Hugo ScHWEITZER and Arthur Zart, Germany. (Bayer.) 
Monoazo dye. 


2-AMINO 5-NAPHTHOL 7-Sulfo or other, coupled with 5.5’-dioxy 2-DINAPHTHYLAMIN 7.7’-disulfo 
in alk. soln. VuioLEer direct and developed (coupled) dyes, which when developed with diazo 4- 
nitranilin are fast to washing and can be discharged white. 

Note 1,009,797. 


1,009,797—Nov. 28, 1911; Hugo ScHWEITZER and Arthur Zart, Germany. (Bayer.) 
Disazo dyestufi. 


I-AMINO 6-NAPHTHOL 3-sulfo, 2 mols., or other, coupled with 5.5’-dioxy 2-DINAPHTHYLAMIN 
7.7/-disulfo in alk. soln. VuioxtEr direct and developed (coupled) dyes, which when developed 
by diazo 4-nitranilin are fast to washing, and can be discharged white. 

Addition to 1,000,796. 


1,009,952—Nov. 28, 1911. Wilhelm Brrcpoit, Germany. (Bayer.) 
Brown azo dye. 


Nitro BENZIDIN coupled in alk. soln. with 1 mol. each of 3-PHENYLENE DIAMIN sulfo and 
PHENOL. Brown direct and developed (coupled) dyes, which can be developed on fiber by diazo 
4-nitranilin to be fast to washing, and to discharge white. 


1,010,433—Dec. 5, 1911. Heinrich Jorpan and Wilhelm NEELMEIER, Germany. (Bayer.) 
Blue trisazo dye. ; 


4-Amino 5-chlor oxalyl ANiIsIDIN or other, coupled with 1-NAPHTHYLAMIN 6-sulfo, rediazo- 
tized and coupled with a second mol. of same, again diazotized and coupled with 1-NAPHTHOL 3- 
sulfo, or other, then saponified. Buus direct and developed (coupled) dyes, that can be diazo- 
tized on fiber and developed with 2-naphthol, then are fast to washing and light, and can be 
discharged white. 

Addition to 1,009,269. 


1,011,770—Dec. 12, 1911. Hugo GELDERMANN, Germany. (Berlin.) 
Azo dye for wool. 


6-Nitro 4-chlor 2-amino PHENOL or other, coupled with 2-NAPHTHOL: 4-sulfo. Buacx acid 
mordant (Cr) dyes. 


1,012,055—Dec. 109, 1911. Marston Bocrert, New York. 
Azo dyestuff. (Process also claimed.) 


2.4-Dioxy QUINAZOLIN (benzoylene urea) or other, coupled with diazo NAPHTHIONIC acid, 
or with a tetrazo comp., etc. Other components claimed. Rep acid, direct or acid mordant dye, 
suitable for lakes. 

Note Ser. 487,695. 


1,012,619—Dec. 26, 1911. Otto Ernst and Heinrich EicHweEpr, Germany. (Hochst.) 
Process of producing dischargeable dyeings on cotton. Direct azo dyes for 
discharge printing. 

2-Amino 5-NAPHTHOL 7-Sulfo acid azo 3-PHENYLENE DIAMIN one mol. as Na salt is padded 
on cotton fiber, dried and passed thru a bath of 2 mols. diazo 4-nitranilin containing sod. acetate 
Other mono azo dyes from amino sulfo acids and a meta diamin capable of being combined with 
one or two mols. diazo 4-nitranilin. are claimed. Red to violet-BRowN or dark BRown developed 
dyes, sol. in aq., fast to washing, and capable of being discharged. 


1,012,853—Dec. 26, 1911. Georg Hotste, Germany. (Bayer.) 
Dye. 

Diamino DIPHENYL urea disulfo dissolved in hot water to which is added 2 mols. melted 
2-, 3- OF 4-nitro BENzOYL chloride. RED, yELLow direct and developed dyes that can be reduced 
to diamino comp., diazotized and coupled on fiber. 


1,012,960—Dec. 26, 1911. Arthur Zart, Germany. (Bayer.) 
Bluish-violet disazo dye. 


BENZIDIN 3.3/-disulfo coupled in alk. soln. with 2 mols. 5.5’-dioxy 2-DINAPHTHYLAMIN 7.7’- 
disulfo. VzioLEer direct dye, fast to ironing. 


GROUP VI.—AZO 161 


1,014,039—Jan. 9, 1912. Melchior Bonicer, Switzerland. (Sandoz.) 
Dark-blue monoazo dyestuffs. (Process also claimed.) 

Brom I-AMINO 2-NAPHTHOL 4-Sulfo coupled in alk. soln. with 2-NAPHTHOL, or other. VIOLET, 
to BLUE or BLACK acid, developed (CrO,) and acid mordant (Cr) dyes, which when chromed 
are fast to potting, milling, carbonizing, and light. 

Note 1,014,114 and reference to use of alcohol, anilin, pyridin, etc., as accelerants to 
coupling reaction. 


1,014,114—Jan. 9, 1912. Melchior BOnicER, Switzerland. (Sandoz.) 
Red monoazo dyestuffs. (Process also claimed.) 


I-AMINO 2-NAPHTHOL 4-Sulfo diazotized, dried and mono brominated in chlor sulfonic acid, 
then coupled in alk. soln. with phenyl methyl PyRAzoLONE or other. ORANGE to VIOLET RED acid, 
developed (CrO,) or acid mordant (Cr) dyes, which when chromed are fast to potting, milling, 
and light. 


1,014,539—Jan. 9, 1912. Ernst Uuricus, Germany. (Wiilfing.) 
Manufacture of lakes. (Product also claimed.) 


I-NAPHTHYLAMIN coupled with 1-NAPHTHOL 4-sulfo acid and pptd. with various substrata to 
form lakes. Rep lakes, fast to light, which cover well and are insol. in aq., alc., and oil. 


1,014,633—Jan. 16, 1912. Wilhelm BrErcpout, Germany. (Bayer.) 
New dye. 


4-Amino ACETANILID coupled with 2-AMINO 5-NAPHTHOL 7-sulfo, saponified, tetrazotized and 
coupled with a second mol. of same and then with PHENOL or other. BLUE to BLACK, direct and 
developed (coupled) dyes that can be diazotized on fiber, and discharged white. 


1,014,9S2—Jan. 16, 1912. Joseph Turner and Harry Dean, England. 
Manufacture of black coloring-matters. 


2- or 4-Chlor ANILIN coupled in mineral acid soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo “‘H’’ 
then combined with tetrazo BENZIDIN, or other, and 1 mol. of 4-chlor 3-PHENYLENE DIAMIN. 
Buack direct dye. 

Note 987,417, 1,014,983, and 4. 


1,014,983—Jan. 16, 1912. Joseph TurNER and Harry Dean, England. 
Manufacture of black coloring-matters. 


BENZIDIN, or other coupled in neutral soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo ““H” then 
combined in alk. soln. with diazo 4-chlor ANILIN (or ortho deriv.) and finally with 4-chlor 3- 
PHEYLENE DIAMIN. Back direct dye. 

Patent differs from 1,014,982 in the order of coupling the components. 


1,014,984—Jan. 16, 1912. Joseph TurNER and Harry Dean, England. 
Manufacture of black coloring-matters. 


4-Amino ACETANILID coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo “Cleves” saponified, rediazo- 
tized and coupled with 2-am1no 8-NaPHTHOL 6-sulfo “‘G’’ again diazotized and coupled with 4- 
chlor 3-PHENYLENE DIAMIN (from dinitro chlor benzol). Buiacx direct dye. 

Addition to 1,014,982. 


1,015,375—Jan. 23, 1912. Arthur Zart, Germany. (Bayer.) 
Azo dye. 


4’-Amino benzoyl 2-AMINO 5-NAPHTHOL 7-Sulfo coupled in acetic soln. with 5.5’-dioxy 7.7’- 
disulfo 2-pINAPHTHYL urea. Other components claimed. ORANGE to RED direct and developed 
dyes, which when developed with diazo 4-nitranilin are fast to washing and discharge white. 

Near S. 279—‘‘Benzo Fast Scarlet.” 


1,016,307—Feb. 6, 1912. Herman WaGNER and Josef Ersper, Germany. (H6chst.) 
Monoazo dyestuff and process of making same. 


I-NAPHTHYLAMIN 2-sulfo coupled with 2-NAPHTHOL 3-carbo. VIOLET dye, suitable for lakes. 
Calcium lake especially beautiful tint. 


162 DIGEST OF PATENTS 


1,019,321—Mar. 5, 1912. Oscar GuntueEr, Germany. (Bayer.) 
Brown tetrazo dye. 


4.4'-Diamino DIPHENYL urea 3.3’-disulfo coupled with 2 mols. 3-PHENYLENE DIAMIN. BRowNn 
direct and developed dye. When developed with diazo 4-nitranilin, is fast to washing and light, 
and can be discharged white. 


1,020,670—Mar. 19, 1912. Paul VotKMANN, Germany. (Bayer.) 
Disazo dye and process of making the same. (Process not claimed.) 

4-Amino ACETANILID coupled in alk. soln. with 1-NAPHTHOL 3-sulfo, saponified and coupled 
with 2-DINAPHTHYLAMIN 5.5/-dioxy 7.7’-disulfo. Process for developing on fiber described. 


Other components claimed. BLuer, vIoLET, RED direct and developed dyes, which when developed 
on fiber with diazo 4-nitranilin give fast shades that discharge white. 


1,020,756—Mar. 19, 1912. Richard Gast, Germany. (Cassella.) 
New cotton dyestuffs and process of making same. 
Phenyl 2-AMINO 5-NAPHTHOL 7-sulfo heated in aq. with Formic acid, Na salt, to form formyl 


phenyl amino compound which is combined in alk. soln. with diazotized suLFANILIC acid azo 4- 
XYLIDIN. Other components claimed. VuIoLET to BLUE direct dyes, fast to acids and light. 


1,021,864—Mar. 26, 1912. Arthur HausporFer and Carl Hrerpenreicu, Germany. (Bayer.) 
Green triphenylmethane dye. 

2.6-Dichlor 5-amino BENZALDEHYDE condensed with 2 mols. 2-crEsoTinic acid, then diazo- 
tized and coupled with phenyl methyl pyrazoLONE. Brown to GREEN, acid and developed (CrO,) 
dyes which when oxidized are fast to fulling, potting and light. 

Addition to 980,251. Patent is classed as azo dye because azo linkage is last formed. 


1,021,365—Mar. 26, 1912. Arthur Hausporrer and Carl HkrpeENREICH, Germany. (Bayer.) 


Yellow-green triphenylmethane dye. Same as 1,021,364 except chlor dibrom instead 
of dichlor deriv. 
2-Chlor 4.6-dibrom 5-amino BENZALDEHYDE condensed with 2 mols. 2-crEsoTiNICc acid, then 
diazotized and coupled with phenyl methyl pyrazoLonr. Brown to yellow GREEN acid and de- 
veloped (CrO,) dyes, which when oxidized are fast to fulling, potting and light. 
Addition to 980,251. Classed as azo dye because of final linkage. 


1,021,366—Mar. 26, 1912. Arthur Hausporrer and Carl Hrempenreicu, Germany. (Bayer.) 
Triphenylmethane dye. Same as 1,021,364 except sulfo group in pyrazolon ring. 
2.6-Dichlor 5-amino BENZALDEHYDE condensed with 2 mols. 2-crEsoTinic acid, then diazo- 
tized and coupled with sulfo phenyl methyl pyRAzoLoNE. Brown to GREEN acid and developed 
(CrO,) dyes, which when oxidized are fast to fulling, potting and light. 
Addition to 980,251. Classed as azo dye because of final linkage. 


1,022,287—Apr. 2, 1912. Arthur Zart, Germany. (Bayer.) 
Azo coloring-matter. 

4’-Amino benzoyl 2-AMINO 5-NAPHTHOL 7-sulfo, 2 mols., coupled with 5.5’-dioxy 2-DINAPHTHY- 
LAMIN 7.7/-disulfo. Rep direct and developed dye, which when coupled on fiber with diazo 
4-nitranilin is fast to washing and discharges white. 

Note 1,022,288. 


1,022,288—Apr. 2, 1912. Arthur Zart, Germany. (Bayer.) 
Azo coloring-matter. : 

4-Amino benzoyl 2-AMINO 5-NAPHTHOL 7-Sulfo coupled with 5.5’-dioxy 2-DINAPHTHYLAMIN 
7.7'-disulfo. Same as 1,022,287 except but one mol. first component used. Rep direct and de- 
veloped dye, which when coupled on fiber with 4-nitranilin is fast to washing and discharges 
white. 

Addition to 1,022,287. 


1,022,612—Apr. 9, 1912. Ernst Uxricus, Germany (Wiilfing.) 
Manufacture of lakes. (Product also claimed.) 


2-TOLUIDIN coupled with 1-NAPHTHOL 4-sulfo. Methods for formation of lakes are described. 
Rep and ORANGE lakes, fast to water, alcohol, oil and light, and cover well. 


GROUP VI.—AzO 163 
1,023,120—Apr. 16, 1912. August Buanx, Germany. (Bayer.) 
Azo dye. 


3-Amino ACETANILID coupled in alk. soin. with 1-AMINO 8-NAPHTHOL 3.6-disulfo, saponified 
then tetrazotized and coupled with REsorciN, 2 mols. or 1 mol. of this and 1 mol. of 3-PHENYLENE- 
DIAMIN. Other components claimed. OLIVE to Brown direct and developed dyes, which when de- 
veloped with diazo-4-nitranilin are fast to washing and light, and give white discharges. 


1,023,199—Apr. 16, 1912. Karl Evser, Germany. (Kalle.) 
Manufacture of a new beta-naphthol-ortho-oxy-azo dye. (Product, not process 
claimed.) 


I-AMINO 2-NAPHTHOL 4-sulfo diazotized, chlorinated in conc. H,SO,, then coupled with 2- 
NAPHTHOL. Rep to BLUE acid and developed (CrO,) dyes, which when oxidized are fast to 
potting and light. 

Note 1,028,006. 


1,024,031—Apr. 23, 1912. H. ScHWeI?Tzer and A. Zart, Germany. (Bayer.) 
Azo dye. 


3'-Sulfamino benzoyl (2)3-TOLUYLENE DIAMIN 5-sulfo by reduction of meta nitro benzoyl com- 
pound with bisulfite, coupled with crEsip1n then condensed in alk. soln. with PHOSGENR to an urea. 
YELLOW to ORANGE direct and developed dye, which when developed on fiber with diazo 4-nitranilin 
is fast to washing. 


) 
1,024,080—Apr. 23, 1912. H. Jorpan and W. NEELMEIER, Germany. (Bayer.) 
Azo dye. 


4-Amino ACETANILID 3-sulfo coupled in acetic soln. with 1-NAPHTHYLAMIN 6-sulfo, rediazo- 
tized and coupled with 2-AMINO 8-NAPHTHOL 6-sulfo, again diazotized and coupled with phenyl 
methyl pYRAZOLONE then saponified. Other components claimed. Green direct and developed dye, 
which when diazotized and developed with 2-naphthol is bluer and fast to light and washing. 


1,024,081—Apr. 23, 1912. H. Jorpan and W. NEELMEIER, Germany. (Bayer.) 
Azo dye. 


Acetyl 4-NAPHTHALENE DIAMIN 6-sulfo coupled in acetic soln. with 1-NAPHTHY1AMIN 6-sulfo 
rediazotized and coupled in alk. soln. with 2-AMINO 8-NAPHTHOL 6-sulfo, again diazotized and 
coupled in acid soln. with methyl KETot (a-methyl indole). Other components claimed. GREEN 
to green-BLUE direct and developed dye, which when coupled on fiber with 2-naphthol is bluer, 
fast to washing and light, and gives white discharge. 


1,024,308—Apr. 23, 1912. Hans BucHerer, Germany. (Kalle.) 
Manufacture of azo coloring-matters containing a carbazole derivative. 
(Product also claimed.) 
2-TOLUIDIN, (or other amin,) or BENZIDIN azo SALICYLIC acid, coupled in alk. soln. with 5-oxy 
7-sulfo 1.2-NAPHTHCARBAZOLE obtained from 2-AMINO 5-NAPHTHOL 7-Sulfo “I” or “G” (2.8.6), 
bisulfite and pHENyL hydrazin. RED, BLUE, VIOLET or BROWN acid and direct dyes, fast to acids. 


1,024,794—Apr. 30, 1912. H. Levinstein and M. Wy er, England. (Levinstein.) 
Manufacture of azo dyestuffs. (Product also claimed.) 


2-NAPHTHYLAMIN coupled in alk. soln. with 2-AMINO 5-NAPHTHOL 7-sulfo urethane derivs. 
Other components claimed. Rep direct dye, fast to light, alk, and mineral acids. 


1,025,267—May 7, 1912. Carl H&eIpENREICH, Germany. (Bayer.) 
Blue wool-dye. 
2-Amino 4-crEso. 6-sulfo coupled with 2-NAPHTHOL. BLUE acid mordant (Cr) dye. 


1,025,983—May 14, 1912. M. Kaun and A. OssensBEcK, Germany. (Bayer.) 


Azo dye. 

BENzIDIN coupled in alk. soln. with 1 mol. of 3-amino PHENOL 4-sulfo and 2 mols. of product 
coupled in neutral soln. with 3.3’-diamino pIPHENYL urea. Other components claimed. ORANGE 
and Brown direct and developed dye, which when diazotized on fiber and coupled with 3-phenylene 
diamin is fast. 

Note 1,025,984. 


164 DIGEST OF PATENTS 


1,025,984—May 14, 1912. M. Kaun and A. OssenBEcK, Germany. (Bayer.) 
Brown azo dye. 


Benzip1n coupled in alk. soln. with 3-PHENYLENE DIAMIN 4-sulfo, and 2 mols. of product 
coupled in neutral soln. with 3.3’-diamino DIPHENYL urea. Other components claimed. ORANGE 
and BROWN direct and developed dyes, which when diazotized on fiber and coupled with 3-phenylene 
diamin, are fast. 

Addition to 1,025,983. 


1,026,902—May 21, 1912. Hans Bucuerer, Germany. (Kalle.) 
Manufacture of azo coloring-matter. (Product also claimed.) 


ANILIN, benzidin, amino azo compounds or other, coupled with 2-AMINO 5-NAPHTHOL 1-sulfo, 
its acyl, benzoyl or urea derivs. or other, in acid or alk. soln. Rep direct and developed dye, that 
can be coupled on fiber. 


1,027,132—May 21, 1912. M. Kaun and A. OssEnNBEcK, Germany. (Bayer.) 
Azo dye. 


6-Nitro 2-amino PHENOL 4-sulfo coupled in alk. soln. with 2-amino BENZIDIN. Brown acid 
and developed (CrO,) dye, which when chromed is fast to potting. 


1,027,148—May 21, 1912. A. OsseENBECK and A. Zart, Germany. (Bayer.) 
Red azo dye. 
6-Chlor 2-ToLuIpIN 4-sulfo coupled with methyl aNnILIN w-sulfo* again diazotized and coupled 


in acetic soln. with benzoyl 2-amino 5-NAPHTHOL 7-sulfo. 
* For mfr. of mono azo deriv., see E. P. 11343-1809. 


1,028,006—May 28, 1912. Karl Exser, Germany. (Kalle.) 

Manufacture and production of fast ortho-oxy-azo dyestuffs. (Product also 
claimed.) Chlorinated 1-amino z-naphthol 4-sulfo azo 1-naphthol or other ortho oxy 
azo comps. 

I-NAPHTHYLAMIN 2-diazo oxid 4-sulfo chlorinated in fuming sulfuric or chlor sulfonic acid 
soln. at 25-50° under pressure with or without a chlorine carrier then condensed in alk. soln. 
with 1-NAPHTHOL. Other components claimed. VioLET and BLUE acid and developed (CrO,) dyes, 
fast when chromed. 


1,028,139—June 4, 1912. A. Scumipt and G. KranzLEIn, Germany. (Hochst.) 


Manufacture of azo dyestuffs of the anthraquinone series and process of 
making same. Anthraquinone azo aceto acetanilid and derivs. 


2-Amino ANTHRAQUINONE 3-sulfo acid or other amino derivs. diazotized and coupled with 
aceto ACETANILID or other aceto acetic aryl amids. Apparently coupling takes place with methyl 
not phenyl group. YELLOW powd. diff. sol. in hot aq. (Y). sol. in cone. sulf. (OR); green YELLOW 
acid dye, fast to aq. and light. 


1,028,140—June 4, 1912. Franz ScHoitt, Germany. (Hodchst.) 
Black disazo dyestuff and process of making same. 


Trimethyl ammonium ANILIN salt coupled with 3-TOLUIDIN, rediazotized and coupled in acid 
soln. with 1.8 or 1.5-diamino NAPHTHALENE. Back basic and direct dye. 
Note 1,029,639. 


1,028,239—June 4, 1912. Ernst Unricus, Germany. (Wiilfing.) 
Color-lake and process of manufacturing same. 


ANILIN coupled with 1-NAPHTHOL 4-sulfo. Process for lake formation with Ca, Ba, Al, etc. is 
given. Rep lakes, fast to water, alcohol, oil and light, and cover well. 
Note 910,030. 


1,028,306—June 4, 1912. Joseph Turner and Harry Dean, England. 
Black coloring-matters. (Process, not product, claimed.) 


BENZIDIN coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo ““H’”’ then combined in alk. soln. with 
diazo 4-chlor ANILIN, finally coupled with 3-PHENYLENE DIAMIN. Other components claimed. 
Buack direct dye. 


GROUP VI.—AZO | 165 


1,028,493—June 4, 1912. Friedrich RUNKEL, Germany. (Bayer.) 
Azo dye. 


4-Amino BENZOPHENONE coupled with 2-NAPHTHOL 3.6-disulfo or 2-naphthol 6-sulfo. Lake 
process described. ORANGE to RED lakes, fast to water and light. 


1,029,639—June 18, 1912. Franz ScHoLt, Germany. (Hdéchst.) 
Black disazo dyestuffs and process of making same. 


Trimethyl ammonium aANILIN salt coupled with 3-ToLuIDIN, rediazotized and coupled with 
I-AMINO 8 Or 5-NAPHTHOL. Other components claimed. Buack basic dye for artificial silk. 
Addition to 1,028,140. 


1,032,412—July 16, 1912. H. Jorpan and W. NEELMEIER, Germany. (Bayer.) 
Blue cotton-dye. 


5-Amino 4-chlor oxalyl ANISIDIN or nitro amino comp., coupled in acetic soln. with 1-NAPHTHY- 
LAMIN 6-sulfo, again diazotized and coupled in alk. soln. with 2-NAPuTHOL 7-sulfo, saponified and 
diazotized and coupled in acid soln. with 1.8-dioxy NAPHTHALENE 4-sulfo. Buiur direct and de- 
veloped dyes, which when developed with diazo-4-nitranilin are fast to washing and give white 
discharge. 


1,032,433—July 16, 1912. Franz ScHoutu, Germany. (Hochst.) 
Black monoazo dyestufis and process of making same. 


Dimethyl pheno SAFRANIN, or other, coupled in acetic soln. with phenyl methyl PYRAZOLONE. 
Buiack basic or basic mordant dye. 


1,032,797—July 16, 1912. Arthur Zart, Germany. (Bayer.) 
Azo dye. 


4’-Amino benzoyl 2-AMINO 5-NAPHTHOL 7-sulfo, 2 mols., coupled in acetic soln. with urea 
from 2 mols. 2-AMINO 5-NAPHTHOL 7-sulfo and PHOSGENE. ORANGE to RED direct and developed 
dye, which when developed with diazo 4-nitranilin is fast to washing, and gives white discharge. 


1033,310—July 23, 1912. Albert Edward Grssiter, New York. 
Monoazo dye. 


I-NAPHTHYLAMIN coupled with 2-NAPHTHOL 7-sulfo. Rep developed dye, suitable for lakes 
and for printing, fast to water, oil, benzol, varnish, light and heat, and will not sublime. 


1,034,853— Aug. 6, 1912. 
A. WintHer, A. I. Lasxa and A. ZitscHER, Germany. (Griesheim.) 
Azo dyes fer lakes. (Process also clamed.) 


s-Nitro 2-TOLUIDIN coupled with 2-oxy 3-NAPHTHOIC acid. Other components claimed. RED 
to ORANGE lakes, fast to oil and light. 


1,034,898—Aug. 6, 1912. Ernst FUSSENEGGER, Germany. (Badische.) 
Azo dyes and process of making the same. 


4-Chlor 2-amino PHENOL coupled in alk., acid or neut. soln. with acetyl 1-AMINO 8-NAPHTHOL 
3.6-disulfo. Other components claimed. Buu direct and developed (CrO,) dye. 


1,038,209—Sept. 10, 1912. Re 13,550—Apr. 1, 1913. 
H. ScHwEeEITzER and A. Zart, Germany. (Bayer.) 
Polyazo dyes. 


4-NITRANILIN 2-sulfo azo I-NAPHTHYLAMIN 7-Sulfo, 2 mols., coupled in alk. soln. with 5.5’-dioxy 
2-DINAPHTHYLAMIN 7.7/-disulfo. Other azo dyes with but one amino and no oxy group are 
claimed. Buivur to vioLET direct and developed dyes, which when developed on fiber with diazo 
4-nitranilin are fast to washing, and discharge white. 


1,038,210—Sept. 10, 1912. H. ScuweitzeErR and A. Zart, Germany. (Bayer.) 
Azo dyes. 


4-NITRANILIN 2-sulfo azo I-NAPHTHYLAMIN 7-sulfo coupled in alk. soln. with 5.5/-dioxy 2- 
DINAPHTHYLAMIN 7.7/-disulfo. Other azo dyes with but one amino and no oxy group are claimed, 


166 DIGEST OF PATENTS 


BLvE to vioLET direct and developed dyes, which when developed on fiber with diazo 4-nitranilin 
are fast to washing and discharge white. 
Patent is same as 1,038,209 except that but one mol. of azo component is used. 


1,038,884—Sept. 17, 1912. W. Herzperc and O. ScHARFENBERG, Germany. (Berlin.) 
Azo dye. 


s-Methoxy 2-nitro 4-TOLUIDIN (or 4-nitro 5-amino 2-CRESOL, methyl ether.) obtained by action 
of sodium methylate on 5-chlor 2-nitro 4-TOLUIDIN, coupled with 2-NAPHTHOL. Rep lake. 


1,041,146—Oct. 15, 1912. C. O. Muuver and A. LurHer, Germany. (Hochst.) 
Dyestuff. 


4-Amino BENZYL sulfo acid coupled in alk. soln. with 4’-amino benzoyl 2-AMINO 5-NAPHTHOL 
7-sulfo, again diazotized and coupled with 2-NAPHTHOL. Yellow-rEp direct dye, fast to acids. 


1,041,919—Oct. 22, 1912. H. Wacner and J. Erser, Germany. (Héchst.) 
Dyestufis and process of making same. 


BENZIDIN 2.2/-disulfo coupled in alk. or acetic soln. with 2 mols. 2’-chlor phenyl methyl prra- 
ZOLONE or the dichlor (2’:5’) product. YELLOW acid dye, suitable for lakes. 


1,042,198—Oct. 22, 1912. Max Cantor, Germany. (Berlin.) 
Red disazo dye. 


2-Amino 4-sulfo DIPHENYL ether coupled in acid soln. with 3-ToLuIDIN, or other, again diazo- 
tized and coupled in alk. soln. with 2-NAPHTHOL 7-sulfo. Or 4-amino 2-sulfo DIPHENYL ether azo 
ANILIN results by condensing the diazo deriv. of first component with TOLHENE sulfone anilid and 
saponifying, or from same in hot NaOH soln. with anilino methane w-sulfo. Rep acid dye. 


1,042,356—Oct. 22, 1912. A. L. Lasxa, A. ZitscHer and F. Kunert, Germany. (Griesheim.) 
Disazo dyes and process of making them. 


DIANISIDIN coupled in alk. soln. with 2 mols. 2-oxy 3-NAPHTHOIC acid anilid. Other com- 
ponents claimed and methods for application to fiber as ingrain dye given. BLACK, BLUE or RED 
developed dyes, suitable for printing and for lakes, which when printed with diazo 4-nitranilin 
give red color. 


1,043,873—Nov. 12, 1912. Franz ScHott and Willy Tropp, Germany. (Héchst.) 
Brown azo dyestuffi and process of making same. 


4-Amino 3/-sulfo N-phenyl azimino BENZENE coupled in alk. soln. with 4-tolyl 2-AmriNno 8- 
NAPHTHOL 6-sulfo or other. Brown acid dye. 


1,045,196—WNov. 26, 1912. Karl ScHIRMACHER, Germany. (Hochst.) 
Azo dyestuff. 


3-Amino 4-methyl pripHENyL sulfone coupled in alk. soln. with phenyl 2-AmINo 8-NAPHTHOL 6- 
sulfo. Brown direct fast dye. 


1,049,109—Dec. 31, 1912. A. L. Lasxa, Germany. (Griesheim.) 
Violet cotton-dyes. 


3.3’-Disulfo 4.4’-diamino DIPHENYL urea coupled in alk. soln. with 2 mols. phenyl 2-aMINo 
5-NAPHTHOL 7-sulfo. VioLET direct dye, fast to light. 


1,051,565—Jan. 28, 1913. Kurt Desamari, Germany. (Bayer.) 
Azo color. 


5-Nitro 2-ANISIDIN coupled in acetic soln. with 2-chlor aceto-ACETANILID produced by heating 
2-chlor ANILIN with aceto acETICc ester in boiling naphtha. Method of forming lakes is described. 
Note 1,059,599 and 1,076,819. 


1,051,859—Feb. 4, 1913. August BLanx, Germany. (Bayer.) 
Trisazo dye. 


2-NAPHTHYLAMIN 3.6-disulfo coupled with 3-rToLUIDIN, recoupled with another mol. of same 
and again coupled with nitro 3-PHENYLENE DIAMIN. Other components claimed. OraANGE to RED 
direct dyes, fast to light. 


GROUP VI.—AZO 167 


1,052,031—Feb. 4, 1913. August Branx, Germany. (Bayer.) 
Trisazo dye. 

2-NAPHTHYLAMIN 3.6-disulfo coupled in acetic soln. with 3-ToLuIDIN, rediazotized and coupled 
with a second mol. of same, again diazotized and coupled in alk. soln. with 2.4-dioxy QUINOLIN. 


Other components claimed. ORANGE to RED direct dye, fast to light. 
Note 1,051,859. 


1,052,135—Feb. A, 1913: 
K. Drsamari, O. GuNTHER, H. SCHWEITZER and A. Zart, Germany. (Bayer.) 
Azo dye. 
1-Amino 6-NAPHTHOL 3-sulfo coupled in very dil. HCl soln. with crresipIN and 2 mols. con- 
densed in alk. soln. with PHOSGENE to an urea comp. Other components claimed. YELLOW, ORANGE 


and red-Brown direct and developed dyes, which when developed by diazo 4-nitranilin are fast 
to light age washing and discharge white. 


1,052,136—Feb. 4, 1913. K. Drsamari and A. Zart, Germany  (Bayer.) 
Disazo dye. 

4-Amino phenyl 5-oxy 7-sulfo 1.2-NAPHTHOXAZOLE or similar naphthimidazol or naphthiazol 
derivs., 2 mols., coupled in alk. soln. with 5.5’-dioxy 2-DINAPHTHYLAMIN 7.7’-disulfo. RED to 


VIOLET direct and developed dyes, which when developed with diazo 4-nitranilin are fast to washing 
and discharge white. 


Note 1,052,137, 1,058,562 and 1,058,692. 


1,052,137—Feb. 4, 1913. K. DesamMari and A. Zart, Germany. (Bayer.) 
Disazo dye. 

4'-Amino C-phenyl 5-oxy 7-sulfo 1.2-NAPHTHIMIDAZOLE, or the similar naphthiazol deriv., 2 
mols. or 1 mol, each of two different components, coupled in alk. soln. with 5.5’-dioxy 7-7'-disulfo 
2-DINAPHTHYL urea. Other components claimed. Rep direct and developed dyes, which when 


_ developed with diazo 4-nitranilin are fast to washing and discharge white. 
Addition to 1,052,136. 


1,052,145—Feb. 4, 1913. Robert Hocustetrer, Ohio. 
Pigment. (Process also claimed.) 


4-Nitro 2-TOLUIDIN coupled in acetic soln. with 2-oxy 3-NAPHTHOIC acid. Rep lake, fast to aq. 


1,052,262—Feb. 4, 1913. H. Levincestern and J. Bappitry, England. (Levinstein.) 
Dyestuffs and their production. 

2-ANISIDIN, benzidin or amino azo comps., etc., coupled in alk. soln. with the glycin ester of 
I-AMINO 8-NAPHTHOL 3.6-disulfo. Mixed dis and trisazo derivs. and various components are 
claimed, always including an ester of a naphthol sulfo glycin. VIOLET, BROWN to BLUE acid and de- 
developed (CrO,) dyes, fast to alkalies and when chromed fast to milling. 


1,052,647—Feb. 11, 1913. Wilhelm Bercpoit, Germany. (Bayer.) 
' Diazotizable coloring-matter. 

Formyl 3-PHENYLENE DIAMIN* coupled in alk. soln. with (2)3-TOLUYLENE DIAMIN 5-sulfo, 
saponified, tetrazotized and coupled with 2 mols. 3-PHENYLENE DIAMIN. Other components claimed. 
' Brown direct and developed dye, which when coupled on fiber with 2-naphthol is fast to washing. 
* Compound is called by patent ‘‘m-amino formyl anilid.’’ Note 1,087,430. 


1,054,34S8—Feb. 25, 1913. Leopold Hrsst, Germany. (Bayer.) 
Wool azo dye. 


I-NAPHTHYLAMIN 5-sulfo or other naphthylamin deriv., coupled in alk. soln. with ethyl 4'-sulfo 
benzyl 3-ToLuIpIN. Other components claimed. YELLOW, RED and vioLET acid dyes, fast to 
washing. 


1,056,0S0—Mar. 18, 1913. Ernst WucK, Germany. (Hochst.} 
Process of produeing dyeings on cotton. Direct azo dyes that discharge white. 


Patent is similar to 1,012,619 with second component of original mono azo dye an aromatic 
dioxy comp. such as 1.8-dioxy NAPHTHALENE 3.6-disulfo, capable of being coupled twice with 


168 DIGEST OF PATENTS 


diazo 4-nitranilin. V1oLeT to BRowN developed dyes, fast to washing and can be discharged pure 
white. 


1,056,493 
Black trisazo dyes. 


Mar. 18, 1913. A. Buank and C. HrmpenrEIcH, Germany. (Bayer.) 


4-Diamino DIPHENYLAMIN coupled in alk. soln. with 2-am1no 8-NaPHTHOL 6-sulfo (or 2.5.7), 
tetrazotized and coupled in alk. soln. with 2 mols. 3-amino PHENYL glycin or with 1 mol. each of 
glycin and of another component. Brack direct and developed dyes, fast to light, which when 
developed on fiber by formaldehyde are fast to washing. 


1,058,562—Apr. 8, 1913. K. Desamari and A. Zart, Germany. (Bayer.) 
Monoazo dye. 


Amino C-phenyl s5-oxy 7-sulfo 1.2-NAPTHIMIDAZOLE or similar oxazole or thiazole, coupled in 
alk. soln. with 5.5’-dioxy 2-DINAPHTHYLAMIN 7.7/-disulfo. Rep direct and developed dyes, which 
when developed on fiber by diazo 4-nitranilin are fast to washing and discharge white. 

Addition to 1,052,136. 


1,058,692—Apr. 8, 1913. A. Zart and K. Desamari, Germany. (Bayer.) 
Monoazo dye. 


4'’-Amino C-phenyl 5-oxy 7-sulfo 1.2-NAPHTHIMIDAZOLE, or similar naphthoxazole or naphthi- 
azole deriv., coupled in alk. soln. with 5.5’-dioxy 7.7’-disulfo DINAPHTHYL urea. Rep direct and 
developed dyes, which when developed on fiber with diazo 4-nitranilin are fast to washing and 
discharge white. 

Addition to 1,052,136 and 7. 


1,059,599—Apr. 22, 1913. Kurt DrsamMari, Germany. (Bayer.) 
Azo dye. 


4-Chlor 2-NITRANILIN coupled in acetic soln. with 2-chlor aceto-ACETANILID. Lake formation 
described YELLOW dye, suitable for lakes, fast to light. 
Addition to 1,051,565. 


1,059,670—Apr. 22, 1913. Georg Hoists, Germany. (Bayer.) 
Dye. : 

4”-Amino benzoyl 4’amino benzoyl diamino sTILBENE disulfo on fiber, diazotized and coupled 
with 2-NAPHTHOL, phenyl methyl pyrazolone, etc. RED, YELLOW, etc. developed fast dyes. 


1,065,950—July 1, 1913. A. Lutuer and C. O. Munzer, Germany. (Héchst.) 
Red azo dyestuffs and process of making same. 


4-TOLUIDIN coupled with 4’-amino benzoyl 3-AMINO 5-NAPHTHOL 7-sulfo, rediazotized and 
coupled in alk. soln. with 4’amino benzoyl 2-amino 5-NAPHTHOL 7-sulfo. Rep direct and developed 
dye that may be coupled on fiber with 2-naphthol. 

Note 888,837 in which second component is a 2.5.7 deriv. while above patent calls for 3.5.7. 


1,067,881—July 22, 1913. Bernhard Ricuarp, Switzerland. (Geigy.) 
Azo dye. (Process also claimed.) 


BENzIDIN coupled with 1 mol. each of 2-NAPHTHYLAMIN 3.6-disulfo and PHENOL, then in alk. 
soln. heated to 30-35° with PHENYL sulfonyl chloride. Other components claimed. Vart-colored 
direct dyes, fast to alk., washing and milling. 


1,071,832—Sept. 2, 1913. H. Wacner and J. Konziwaas, Germany. (Héchst.) 
Color-lakes. 


2.2'-TOLIDIN coupled with 2 mols. 2-NAPHTHOL 3.6-disulfo and pptd. as lake. Rep lakes. 
Note 1,071,833. 


1,071,833—Sept. 2, 1913. H. Wacner and J. Konziwaas, Germany. (Hochst.) 
Red wool dyestuff and process of making same. 


2.2/-TOLIDIN coupled in alk. soln. with 2 mols. 2-NaPHTHOL 6-sulfo. Rep direct dye, fast to 
milling. 
Addition to 1,071,832. 


GROUP VI.—AZO 169 


1,073,754—Sept. 23, 1913. Peter Hauptmann, Germany. (Bayer.) 
Azo dye. 


4-Amino benzyl pyripIN or other, coupled in alk. soln. with 2.4-dioxy QUINOLIN. YELLOW 
direct dye, fast to light. 
Note 1,074,946. 


1,073,784—Sept. 23, 1913. Otto SIEPERMANN, New Jersey. (Consolidated.) 
Manufacture of coloring-matters. (Product also claimed.) 


2-NAPHTHYLAMIN 1-sulfo coupled in acid soln. with a second mol. of same, rediazotized and 
coupled in alk. soln. with 2-NAPHTHOL. Rep dye for lakes, fast to aq., oil, light and lime. 


1,073,902—Sept. 23, 1913. P. Junius and C. IMMERHEISER, Germany. (Badische.) 
Azo dye. 


3-TOLUBDIN coupled in alk. soln. with benzoyl 1-AMINO 8-NAPHTHOL 4.6-disulfo. Rep dye for 
lakes. 
Note 1,073,903 to 5 and 1,073,951. 


1,073,903—Sept. 23, 1913. P. Junius and C. IMMERHEISER, Germany. (Badische.) 
Azo dye. 


3-XYLIDIN coupled in alk. soln. with benzoyl 1-AMINO 8-NAPHTHOL 4.6-disulfo. Rep dye for 
lakes. 
Addition to 1,073,902. 


1,073.904—Sept. 23, 1913. P. Junius and C. IMMERHEISER, Germany. (Badische.) 
Azo dye. 


2-ANISIDIN or other amino phenol alkyl ethers coupled in alk. soln. with benzoyl 1-amINno 8- 
NAPHTHOL 4.6-disulfo. Rep dye for lakes. 
Addition to 1,073,902. 


1,073,905—Sept. 23, 1913. P. Junius and C. IMMERHEISER, Germany. (Badische.) 
Azo dye. 


_ I-NAPHTHYLAMIN coupled in alk. soln. with benzoyl 1-aMINo 8-NAPHTHOL 4.6-disulfo. VurIoLeEt 
dye for lakes. 
Addition to 1,073,902. 


1,073,951—Sept. 23, 1913. L. Buancty and C. IMMERHEISER, Germany. (Badische.) 
Azo dye. 


3-Chlor ANILIN, or other amino comp. free of sulfo, carbo or hydroxyl groups, coupled in alk. 
soln. with 2’.4/-dichlor benzoyl 1-AMINO 8-NAPHTHOL 4.6-disulfo or other halogen deriv. with one 
halogen substituent in benzene nucleus. Rep to vioLet dyes for lakes. 

Addition to 1,073,902. 


1,074,429—Sept. 30, 1913. Oscar GUNTHER, Germany. (Bayer.) 
Azo coloring-matter. 

4-Amino ACETANILID coupled with 4’-amino benzoyl 2-AMINO 5-NAPHTHOL 7-sulfo rediazotized_ 
and coupled with rEsorcIN. Other components claimed. ORANGE to RED direct and developed 
dyes, fast to acids and to washing after treatment with formaldehyde. 


1,074,946—Oct. 7, 1913. Peter Hauptmann, Germany. (Bayer.) 
Azo dye. 


4’-Amino benzyl pyripin, or other, coupled in acetic soln. with crEsiIpIN, rediazotized and 
coupled in alk. soln. with 2.4-dioxy Qguinotin. Other components claimed. RED to Brown basic 
and direct dyes, fast to aq. 

Addition to 1,073,754. 


1,075,134—Oct. 7, 1913. Ernst ZEHNTNER, Switzerland. (Durand.) 
Disazo dyestuffs and process of making same. 


BENZIDIN 2.2’-disulfo coupled with 2 mols. saLiIcyLic acid, or other oxycarbo acid. YELLOW 
direct and acid mordant dyes, suitable for printing, easily soluble, fast to soap, soda, Cl, light 
and washing. 

Note 329,638 and 394,841. 


170 DIGEST OF PATENTS 


1,075,3805—Oct. 7, 1913. Otto ScuMipt, Germany, (Badische.) 
Azo dyes and process of making the same. 


5-Chlor 2-NITRANILIN coupled in acid soln. with 1.3-diketo hydro INDENE or derivs. Other 
components claimed. YELLOW to RED acid and developed (CrO,) dyes, suitable for lakes, fast 
to light, aq., alc., and oil. 


1,076,321—Oct. 21, 1913. K. ScHIRMACHER and H. Exvert, Germany. (Hochst.) 
Brown azo dyestufis. 


4’-Tolyl 4-amino PHENYL sulfid obtained by reduction of sulfoxid produced from an aromatic 
sulfinic acid and aromatic base, coupled in alk. soln. with phenyl 2-aMINO 8-NAPHTHOL 6-sulfo. 
Fast BROWN acid dye. 

Note 1,077,492. 


1,076,756—Oct. 28, 1913. Ernst FusSsENEGGER, Germany. ,(Badische.) 
Azo dyes. 


4-NITRANILIN coupled in acid soln. with 2-AMINO 8-NAPHTHOL 3.6-disulfo, reduced with Na,S, 
and condensed in alk. soln. with PHOSGENE to an urea. Rep direct dyes, fast to light. 


1,076,819—Oct. 28, 1913. Heinrich CLINGESTEIN, Germany. (Bayer.) 
Azo colors suitable for use as pigments. 


2-Chlor ANILIN coupled in acetic soln. (neutral to Congo paper) with aceto acet 4-ANISIDID. 
Other components claimed and lake formation described. YELLOW to GREEN lakes, fast to light. 
Note 1,051,565. 


1,077,492—Nov. 4, 1913. K. ScHIRMACHER and H. Evert, Germany. (Hdéchst.) 
Brown azo dyestufis. 


Tolyl 4-amino PHENYL sulfoxid coupled in alk. soln. with phenyl 2-AMINO 8-NAPHTHOL 6-sulfo. 
Other components claimed. Brown acid dye, fast to washing. 
Addition to 1,076,321. 


1,078,504—WNov. 11, 1913. W. Herzperc and W. Lance, Germany. (Berlin.) 
Diazotizable disazo dyes for cotton. (Process also claimed.) 


SULFANILIC acid, 2 mols., coupled with 3.3’-diamino DIPHENYL urea, condensed in alk. soln. 
with 2 mols. 3-nitro BENzoyL chloride then reduced in acetic soln. with Na,S, at 90°. Other com- 
ponents claimed. YELLOW, ORANGE and RED direct and developed dyes, which when coupled on 
fiber with 2-naphthol are fast to washing. 

Addition to 1,078,503. 


1,078,503—Nov. 11, 1913. W. HeErzperc and W. Lance, Germany. (Berlin.) 
Diazotizable disazo dyes for cotton. (Process also claimed.) 


SULFANILIC acid coupled in acetic soln. with 3.3’-diamino DITOLYL urea then combined with 
diazo ANILIN. Other components claimed, one being a basic amin and the other an amino acid. 
YELLOW to ORANGE and BROWN direct and developed dyes, that can be coupled on fiber with 2- 
naphthol and then are fast to washing. 


1,078,925—Nov. 18, 1913. M. Kaun and A. Ossrenspeck, Germany. (Bayer.) 
Black mordant monoazo dyestuff. 


4-Chlor 2-amino PHENOL 6-sulfo coupled in alk. soln. with acetyl 1-am1No 7-naphthol. Other 


components claimed. VuioLET and sLack acid mordant and developed (CrO,) dyes, which when 
chromed are fast to light and fulling, and may be dyed by one bath method. 


1,078,926—Nov. 18, 1913. M. Kaun and A. OssenBEcK, Germany. (Bayer.) 
Blue azo dyes. 

Oxalyl 4-PHENYLENE DIAMIN sulfo, 2 mols., coupled in alk. soln. with one mol. 5.5’-dioxy 2- 
DINAPHTHYLAMIN 7.7’-disulfo, saponified, tetrazotized and coupled with 2 mols. 3-PHENYLENE 
DIAMIN. Other components claimed. BuuE and sBiack direct and developed dyes, that can be 
developed on fiber with diazo 4-nitranilin. 


1,079,415—Nov. 25, 1913. G. Kariscuer, Germany. (Cassella, N. Y.) 
Disazo dyes and processes of making same. 


2-AMINO 5-NAPHTHOL 7-sulfo coupled in acetic soln. with crEsIDIN, rediazotized and coupled 
in alk. soln. with phenyl 2-AMINO 5-NAPHTHOL 7-sulfo. Other components claimed. BtvueE to 


GROUP VI.—AZO I7I 


vIoLET direct and developed dyes, which when developed on fiber by diazo 4-nitranilin are bluer, 
fast to washing and light, and discharge white. 


1,082,581—Dec. 30, 1913. A. Buanx, C. Herpenreicu and J. Jansen, Germany. (Bayer.) 
Cotton-dyestuffs. 


3.3’-Diamino DIPHENYL urea coupled in alk. soln. with 2-AMINO 8-NAPHTHOL 6-sulfo, again diazo- 
tized and coupled with 2 mols. 3-PHENYLENE DIAMIN or 1 mol. each of two components. Other 
components claimed. Brown direct and developed dyes, which when developed on fiber with 
formaldehyde are fast to washing. 


1,082,719—Dec. 30, 1913. H. Wacner, Germany. (Hichst.) 
Monoazo dyestuffs and process of making same. 


4-NITRANILIN or other mono or di nitro aryl amin coupled in alk. soln. with aceto ACETANILID. 
YELLOow lakes, fast to light, oil, alc., light and lime. 


x 
1,082,923—Dec. 30, 1913. A. BLANK and W. BeErcpout, Germany. (Bayer.) 
Azo dyestuffs.: 


DIANISIDIN coupled in alk. soln. with 1 mol. each of 1.8-dioxy NAPHTHALENE 3.6-disulfo and 
5.5’-dioxy 2-DINAPHTHYLAMIN 7.7/-disulfo. Other components claimed. Buus direct dyes. 
Note 1,087,429. 


1,082,924—Dec. 30, 1913. A. Buanx, C. HEIpENREICH and J. JANSEN, Germany. (Bayer.) 
Cotton-dyestuffs. 


3-3’-Diamino dibenzoyl diamino disulfo sTILBENE coupled with 2 mols. RESORCIN, or other. 
YELLOW to orange-RED direct dyes fast to washing when after treated with formaldehyde. 


1,082,925—Dec. 30, 1913. A. Buank, C. HEIDENREICH and J. JaANsEN, Germany. (Bayer.) 
Cotton-dyes. 


4.4’-Diamino dibenzoyl diamino DIPHENYL urea disulfo coupled with 2 mols. RESORCIN, or other, 
or with 1 mol. each of two components. YELLOW to RED direct and developed dyes which when de- 
veloped on fiber with formaldehyde are fast to washing. 

Addition to 1,012,853. 


1,084,363—Jan. 13, 1914. Rudolph RryHER, Germany. (Griesheim.) 
Yellow monoazo dyes and process of making them. ; 


2.6-XYLIDIN or its sulfo acids coupled in alk. soln. with 2’-chlor 5’-sulfo phenyl PYRAZOLONE 
carbo acid. Other components claimed. Green-yELLOW acid dye, fast to light. 


1,086,155—Feb. 3, 1914. Hugo GELDERMANN and Fritz ACKERMANN, Germany. (Berlin.) 
Yellow azo dyes. 


2-NITRANILIN 4-sulfo coupled in acetic soln. with aceto ACETANILID, or other. Green-YELLOW 
lakes, fast to light, oil, aq., and alc. 


1,087,427—Feb. 17, 1914. August BLANK and Matthias LarrEn, Germany. (Bayer.) 
Basie azo dyes. 


Amino benzyl pyrip1INn coupled with cRESsIDIN then condensed in acetic soln. with PHOSGENE to 
an urea. Other components claimed, the azo dye employed being free from salt forming groups. 
YELLOW to RED direct and basic dyes, fast to washing. 

Note 1,087,428. 


1,087 ,428—Feb. 17. 1914. August BLanx and Matthias LarrEn, Germany. (Bayer.) 
Dyes derived from aminotrisazo compounds, 


Amino azo BENZENE disulfo coupled with 3-rToLUIDIN, rediazotized and coupled with a second 
mol. of same, then in alk. soln. condensed with PHOSGENE to an urea. Other components claimed. 
Brown direct dye, fast to light. 

Note 1,087,427. 


1,087,429—Feb. 17, 1914. August BLanx and Wilhelm Brercuortpt, Germany. (Bayer.) 
Azo dyes. 


4-Amino ACETANILID coupled with 1.8-dioxy NAPHTHALENE 3.6-disulfo, saponified, rediazotized 
and coupled with 5.5’-dioxy 7.7’-disulfo 2-DINAPHTHYLAMIN urea. Other components claimed. 
Green-BLUE direct dye for artificial silk, half-silk or half-wool (wool untinged even at boil). 
Note 1,087,923, 1,087,430 and 1,090,379. 
12 


v7 DIGEST OF PATENTS 


1,087,430—Feb. 17, 1914. 
August Bianx, Carl HrmpENrIcH, and Johannes JansEeN, Germany. (Elberfeld.) 
Cotton-dyestuffs. 


3-Amino FORMANILID, 2-mols., coupled in alk. soln. with 5.5’-dioxy 7.7’-disulfo 2-DINAPHTHY- 
LAMIN urea, saponified, tetrazotized and coupled with 2 mols. REsorRcIN. RED to BLUE direct and 
developed dyes, which when developed on fiber by formaldehyde are fast to washing. 

Addition to 1,089,429. 


1,088,735—Mar. 3, 1914. Hugo ScHwEertzer and Arthur Zart, Germany, (Bayer.) 
Blue dyestuif. 


4-NITRANILIN 2-sttlfo azo I-NAPHTHYLAMIN 7-sulfo coupled in alk. soln. with 5.5’-dioxy 7.7’- 
disulfo 2-DINAPHTHYLAMIN, then combined with diazo 2-AMINO 5-NAPHTHOL 7-sulfo. Other com- 
ponents claimed and process for dyeing and developing described. Buiur direct and developed 
dyes, which when developed on fiber with diazo 4-nitranilin are fast to washing and light, and 
discharge white. 

Addition to 1,038,209 and tro. 


1,090,379—Mar. 17, 1914. 
August Bianx, Carl HrerpEnricu and Johannes JansEN, Germany. (Elberfeld.) 
Cotton-dyes. 


4-Amino ACETANILID, 2 mols., coupled in alk. soln. with 5.5’-dioxy 7.7’-disulfo 2-DINAPHTHY- 
LAMIN urea, saponified, tetrazotized and coupled with 2 mols. REsoRCIN, or other aryl deriv. having 
auxochrome groups in meta position. Other components claimed. Buiug direct and developed 
dyes, which when developed on fiber by formaldehyde are fast to washing. 

Addition to 1,087,429. 


1,091,148—Mar. 24, 1914. August L. Lasxa and Arthur Zitscurer, Germany. (Griesheim.) 
Disazo dyestuff. (Process also claimed.) 


2.5.2’.5’-chlor BENZIDIN coupled with 2 mols. 2/.5’-dichlor phenyl methyl pyrazoLone or other. 
Green-YELLow lakes, fast to water, oil and light. 


1,092,842—Apr. 14, 1914. Herbert ‘LevINSTEIN and James Bappit£y, England. (Levinstein.) 
Azo dyestuffs and their production. 


2-NAPHTHYLAMIN 6-sulfo or other, coupled with phenyl amino acetyl 2-AMINO 5-NAPHTHOL 
7-sulfo or meta nitro phenyl compound (which can be reduced) or other. Or 2-naphthylamin 3.6- 
disulfo coupled with 4-xyi1p1n followed by anilid of glycin of 2-AMINO 5-NAPHTHOL 7-sulfo. Red, 
green-BROWN or BLACK direct and developed dyes, fast to acids and light, which when chromed 
are faster to milling, potting and light. 


1,094,448—Apr. 28, 1914. August L. Lasxa, Germany. (Griesheim.) 
Yellow disazo dyes for cotton and process of making them. 

2.2'-Dichlor BENZIDIN or other, coupled with 2 mols. 3-amino phenyl pyRAzOLONE carbo, or with 
the nitro phenyl product that may later be reduced. Yellow and orange-rEp direct and developed 
dyes that may be coupled on fiber with 2-naphthol. 


1,097,231—May 109, 1914. Heinrich Jorpan and Wilhelm NeELMeErER, Germany. (Bayer.) 
Azo dyestuffs. 

3’-Amino 4/-anisoyl 4-amino sSALicyLic acid coupled with 1-NaPpHTHOL 4-sulfo. Other com- 
ponents claimed. YELLOW to RED to VIOLET dyes, that may be printed on fiber as chrome lakes, and 
are fast to Cl and soap. 


1,098,388—June 2, 1914. Heinrich Jorpan and Wilhelm NEELMEIER, Germany. (Syn.) 
Red azo dye. 

4’-Amino benzoyl 4-amino 2.6-crEsoTINIC acid, coupled in alk. soln. with 4’-sulfamino ben- 
zoyl 2-AMINO 5-NAPHTHOL 7-sulfo. Other components claimed. Rep direct and developed dyes, 
fast to light and soap and can be coupled on fiber with 2-naphthol. 


1,099,108—June 2, 1914. 
Adolf Wintuer, August L. Lasxa, Arthur Z1rscuer, 
Felix Kunert and Edwin Acker, Germany. (Griesheim.) 
Producing ice colors. ‘ 
Fiber is impregnated with hot soln. of 2.3-oxy Naputuorc acid anilid, or other arylamino 
deriv. of this acid or its substitution products, then passed through an acetic acid bath of a 


GROUP VI.—AZO 173 


coupling agent such as 5-nitro 2-roLUIDIN, Though patented as an application to fiber, dye is 
new in this form. 
Note 1,034,853, 1,042,356, and 1,127,027 (A). 


1,099,676—June 9, 1914. Joseph Turner and Harry Dean, England. (Holliday.) 
Substantive dyestuffs. 


BENZzIDIN coupled with 1 mol. each of saLicyLic acid and 1-NAPHTHYLAMIN 6-sulfo, rediazo- 
tized and coupled with 2-AMINO 8-NAPHTHOL 6- or 7-sulfo ‘‘G” or “J.’”? Other components claimed. 
Gray and BLACK direct dyes. 


1,101,739—June 30, 1914. Oskar GuntuER and Arthur Zart, Germany. (Synthetic.) 
Azo dyestuffs. 

2-NAPHTHYLAMIN 5-sulfo coupled with 1-AMINO 5-NAPHTHOL 7-sulfo which has been acetyl- 
ized in OH group, rediazotized and coupled with 4-amino benzoyl 2-AMINO 5-NAPHTHOL 7-sulfo. 
Other components claimed. BLUE, BLACK and GREEN direct and developed dyes, that can be 
coupled on fiber with methyl phenyl pyrazolone or with diazo 4-nitranilin. 


1,106,781—Aug. 11, 1914. Edward S. Cuapin and Emil Lesser, Massachusetts (Amer. Dye.) 
Dyestuffs and proecsss of manufacturing the same. 


SuULFANILIC acid, or other amino sulfo acid, coupled in alk. soln. with a-anhydro tetra 
methyl HEMATOXYLONE (Herrig, Monatsch, 1895, 16, 909; and Perkin, Trans. 1902, 81, 1008). 
Other components claimed. Rep, vioLET, and BROWN acid dyes. 


1,107,164—Aug. 11, 1914. Richard Herz, Germany. (Cassella, New York.) 
Producing fast dyeings on the fiber. 


PRIMULIN (4 per cent) dyed as usual then diazotized on fiber and developed in acid bath 
with tetramino CARBAZOLE (14-1 per cent) or derivs. VARI-coLoRED developed dyes, fast to light, 
washing, milling, etc. Though presented in form of dyeing on fiber, dye is new. 


1,113,468—Oct. 13, 1914. Carl Mtuuer, Germany. (Kalle.) 


Manufacture of an azo dyestuff which may be developed on the fiber. 
(Product also claimed.) 


I-NAPHTHYLAMIN 2-Sulfo coupled in neutral soln. with 1-NAPHTHYLAMIN, rediazotized and 
coupled in alk. soln. with 2-AMINO 5-NAPHTHOL 7-sulfo. Blue-vioLET direct and developed dye, 
which when coupled with 2-naphthol is fast to washing. 


1,113,622—Oct. 13, 1914. Peter HauptMANN and Albert Ruopr, Germany. (Synthetic.) 
Azo dyes for wool. 


4’-Amino benzoyl DIPHENYLAMIN, coupled in acid soln. with 2-methyl 1npDoLE 6-sulfo. Other 
components claimed. YELLOW to RED acid dyes, fast to light and milling. 


1,114,750—Oct. 27, 1914. Karl Hacemann, Germany. (Synthetic.) 
Yellow azo dye. 


4'Amino benzoyl 2-amino 4-chlor pHENoL 6-sulfo coupled with 2-methyl 1NDoLE. YELLOW 
acid mordant (Cr acetate) dye, fast to light and milling, and useful for printing.. 


1,114,771—Oct. 27, 1914. Heinrich Jorpan and Wilhelm N&e_MErER, Germany. (Bayer.) 
Monoazo dyestuffs. 
4-Amino 6-methyl saLicyLic acid coupled in alk. soln. with acetyl 1-AMINO 8-NAPHTHOL 3.6- 


disulfo. Other components claimed. Rep, vioLEt or BLUE acid mordant (Cr) dyes, fast to Cl 
and soap. 


1,114,844—Oct. 27, 1914. Arthur Zart and Hugo ScuweitzerR, Germany. (Synthetic.) 
Azo dyes. 


3’-Nitro benzoyl 4-PHENYLENE DIAMIN 3-sulfo coupled in alk. soln. with dehydro thio sulfo 
tolyl methyl pyrazoLtonse (or sulfo tol thiazole phenyl methyl pyrazolone). Other components 
claimed. Yxrtuow direct and developed dyes, which when coupled on fiber with beta naphthol 
are fast to washing. 

Note 1,125,075 (Desamari). 


174 DIGEST OF PATENTS 


1,120,700—Dec. 15, 1914. Paul Euriicu and Paul Karrer, Germany. (Héchst.) 
Arseno-azo compounds and process of making same. 


See group xxiv (m) Medicinal Compounds for process. Not used as dye. 


1,121,026—Dec. 15, 1914. August L. Lasxa and Arthur ZirtscHEer, Germany. (Griesheim.) 
Azo dyes from the arylamids of 2.3-oxynaphthoic acid and process of 
making them. 
2-Amino ANTHRAQUINONE, the diamino product, or other, coupled with anilid of 2-oxy 3- 
NAPHTHOIC acid or other (1-2 mols.). Methods for development on fiber and for lakes given. 
Rep developed dyes, fast to soap and light. Lakes fast to oil and light. 


1,122,564—Dec. 29, 1914. 
Arthur ZitscHEer, Felix KuHNErt and Edwin Acker, Germany. (Griesheim.) 
Condensation products from the arylamids of 2.3-oxynaphthoic acid and 
formaldehyde and azo dyestuffs therefrom and process of making same. 
Anilid of 2-oxy 3-NAPHTHOIC acid, or other, condensed in alk. soln. with FORMALDEHYDE, 
then combined with diazo-4-nitro 2-ToLUIDIN, dianisidin or other amin, diamin or amino azo 
body. Processes for application and other components given. RED to BLACK (coupled) dyes, 
suitable for lakes, fast to rubbing, soap, light and Cl. 


1,123,263—Jan. 5, 1915. Heinrich E1cHweEp£, Germany. (Héchst.) 
Process of producing dyeings on cotton. 


2.6-TOLUYLENE DIAMIN 4-Sulfo, or other tetrazo diamin, coupled with 2 mols. 4/-amino phenyl 
methyl pyRAZOLONE or’ one mol. of this and one of another coupling agent. ‘Though given 


as an application to fiber, dye is new. YELLOW to ORANGE to BROWN developed dyes, both fast 
and easily discharged. 


1,123,430—Jan. 5, 109015. Willy Tropp, Germany. (Héchst.) 
Red wool-dyestuffs. 


4-NITRANILIN 2-sulfo, coupled in acid soln. with 2-AMINO 8-NAPHTHOL 6-sulfo, reduced in 
alk. soln. and acetylated. Rep acid dye, fast and even. 


1L,125,050—Jan. 19, 1915. 
August Bianx, Carl HEIpENRICH and Johannes JANSEN, Germany. (Synthetic.) 
Blue trisazo coloring-matter. 


Oxalyl 4-PHENYLENE DIAMIN, or nitro amin, coupled in alk. soln. with 1-NAPHTHYLAMIN 
7-sulfo, rediazotized and coupled with a second mol. of same, again diazotized and coupled 
with rEsorcIN, finally saponified. Other components claimed. Buus direct and developed 
dye, which when developed with formaldehyde is fast to washing. 


1,125,073—Jan. 10, 1915. Kurt Dresamari, Germany. (Synthetic.) 
Azo coloring-matter. 

4-Amino phenyl PHENTHIAZOLE carbo acid (from acetyl dehydrothio ToLUIDIN by oxida- 
tion and saponification) coupled with aceto ACETANILID 4-carbo or other. Green-yELLow direct 
dye. 

Note 1,114,844 (Zart-Schweitzer) and 1,125,074. 


1,125,074—Jan. 19, 1915. Kurt Drsamari, Germany. (Synthetic.) 
Azo dye. | 
4’-Amino phenyl PHENTHIAZOL sulfo carbo acid (same as 1,125,073 with added meta sulfo 


group) coupled with aceto ACETANILID, or other. 
Addition to 1,125,075. 


1,126,413—Jan,. 26, 1915. Kurt Drsamari, Germany. (Synthetic.) 
Azo dyestuff. 


2-Nitro 4-TOLUIDIN coupled in alk. soln. with aceto ACETANILID 4-carbo. Other components 
claimed. Green-yELLOW lakes. 


GROUP VI.—AZO 175 


1,126,466—Jan. 26, 1915. Martin Herzperc, Germany. (Synthetic.) 
Azo dyestuffs. 

4.4’Diamino DIPHENYL urea, or dimeta comp. coupled with 1 mol. each of 2-amino 8- 
NAPHTHOL 6-sulfo, and REsoRcIN. Other components claimed. Brown to RED direct and de- 
veloped dyes, rendered fast to washing and light by after treatment with formaldehyde. 


1,126,489—Jan. 26, 1015. Richard Korur and Oscar DresseL, Germany. (Synthetic.) 
Azo dyes. 
ANILIN or other, coupled with condensation product of sulfonyl chloride of sauicy4ic 


acid and I-AMINO 8-NAPHTHOL 3.6-disulfo, or other. RED to ORANGE to vIOLET acid and devel- 
oped (CrO,) dyes, which when chromed are bluer and fast to milling, washing and printing. 


1,126,656—Jan. 26, 1915. Hans REINDEL, Germany. (Badische.) 
Azo dyes. 
BENZIDIN, or dipara diamino diphenyl urea, or other, coupled in alk. soln. with 1 mol. each 


of PHENOL 3-sulfo, or other, and 2-AMINO 5-NAPHTHOL 7-sulfo, or other. RED to GREEN direct 
dyes. 


1,127,284—Feb. 2, 1915. Karl HacemMann, Germany. (Synthetic.) 
Monoazo dyestuffs. 
4’-Toluidin 3’-sulfonyl 4-chlor 2-amino PHENOL 6-sulfo coupled with 2’-chlor 5/-sulfo phenyl 


methyl PYRAZOLONE. Other components claimed. YELLOw acid mordant dye, fast to milling 
and light. 


1,127,261—Feb. 2, 1915. Heinrich Jorpan and Wilhelm NeEe_meEieR, Germany. (Synthetic.) 
Azo dyes. 
4-Amino BENZIMIDAZOLE WN-salicylic acid coupled in alk. soln. with acetyl 1-Am1No 8-NAPH- 


THOL 4.6-disulfo, or other. YELLOW to RED to VIOLET acid mordant (Cr acetate) dyes, fast to 
Cl and soap. 


1,129,815—Feb. 16, 1915. Wilhelm NEELMEIER and August S1cwart, Germany. (Synthetic.) 
Azo dyes. 

2-SULFANILIcC acid coupled in alk. soln. with 2-NAPpHTHOL 6-sulfonyl phenyl ether. ORANGE, 
RED, BLUE and sLacK acid or developed (Cr acetate) dyes, fast to milling and bluer when 
chromed. 

Note 1,129,814. 


1,129,814—Feb. 16, 1915. Wilhelm NEELMEIER and August Sicwart, Germany (Synthetic.) 
Azo coloring-matters. 

2-NAPHTHOL 1-carbo 6-sulfonyl chloride, or other, condensed with 1-AMINO 8-NAPHTHOL 4.6- 
disulfo, or other, then combined in alk. soln. with two mols. diazo ANILIN. RED, BLUE and 
BLACK acid dyes, fast to light, sulfur and milling. 

Addition to 1,128,813. 


1,145,072—July 6, 19015. August L. Lasxa and Arthur ZirscuEr, Germany. (Griesheim.) 
Azo dyestufis insoluble in water and process of making them. 


_ 4-Nitro 1.2-ANISIDIN, or other, coupled with benzoyl 2-AMINO 3-NAPHTHOL, or other. Method 
for development on fiber given. Rep developed dye suitable for lakes which are fast to oil. 


1,147,803—July 27, 1915. Heinrich Jorpan and Wilhelm NEELMEIER, Germany. (Synthetic.) 
Azo coloring-matters. 

4”.4'' Diamino dibenzoyl 4.4/-diamino 3.3’-disulfo DIPHENYL urea, or other, coupled in 
alk. soln with 2 mols. 3-amino phenyl methyl pyraAzoLoNE. YELLOW to ORANGE direct and de- 
veloped dyes, made fast to washing by treatment with formaldehyde. Can be coupled on fiber. 


1,149,231—Aug. 10, 1015. 
Hermann Wacner, Josef ErsEr and Erwin Horra, Germany. (Hochst.) 
Yellow ehrome-mordanrt dyestuffs and process of making same. 


5-Chlor ANTHRANILIC acid, or other, coupled with 2-chlor 5’-sulfo phenyl methyl pyrazo- 
LONE, or other. YrELLow acid mordant dye. 


176 DIGEST OF PATENTS 


1,150,656—Aug. 17, 1015. 
August BLrank, Carl HrmpENRIcH and Johannes Jansen, Germany. (Synthetic.) 
Azo dyestufis. 


Oxalyl 4-PHENYLENE DIAMIN Sulfo coupled in acetic soln. with 1-AMINO 2-NAPHTHOL ethyl 
ether, rediazotized and coupled in alk. soln. with 3’-amino phenyl 5-oxy 7-sulfo 1.2-NAPH- 
THIMIDAZOLE, again diazotized and coupled with REsoRcIN, then saponified. Other components 
claimed. GREEN direct and developed dyes which by formaldehyde treatment are rendered 
fast to washing. 


1,150,675—Aug. 17, 1915. Oskar GUNTHER, Germany. (Synthetic.) 
Azo dyestufis. 


2.5-Dichlor ANILIN 4-sulfo, coupled in alk. soln. with 1-AMINO 2-NAPHTHOL 6-sulfo ethyl 
ether, rediazotized and coupled in NH, soln. with 4’-amino benzoyl 2-AMINO 5-NAPHTHOL 7-Ssulfo. 
Other components claimed. BLukE to GREEN direct and developed dyes that can be coupled on 
fiber with pyrazolone, or other, or with diazo 4-nitranilin, etc. 


1,150,825—Aug. 17, 1015. Felix KLINGEMANN, Germany. (Cassella, N. Y.) 
Claret-red trisazo dyestuff. 


3/PHENYLENE DIAMIN aZO 2-AMINO 5-NAPHTHOL 7-sulfo coupled with 2 mols. RESORCIN. RED 
direct and developed dye, which when treated with formaldehyde is fast to wsahing. 


1,153,555—Sept. 14, 1915. Herbert LtvinstrE1In and James BappitEy, England. (Levinstein.) 
Azo dyestufis. 


3’Amino benzoyl 4-PHENYLENE DIAMIN, meta diamin compound: or other, coupled with 2 
mols. RESORCIN, or 1 mol. of this with another coupling agent. See examples and lists of com- 
ponents. ORANGE, YELLOW and rep direct and developed dyes, which after treatment with 
formaldehyde are fast to soap and cross dyeing. 


1,154,826—Sept. 28, 1915. Otto WuLFr, Germany. (Hd6chst.) 
Red wool dyestuffs and process of making same. 


ANILIN 2-sulfo coupled in acetic soln. with 2-AMINO 8-NAPHTHOL 6-sulfo. Rep acid dye, 
fast to light. 


1,155,765—Oct. 5, 10915. Otto StaEHLIN, Germany. (Hdéchst.) 
Mordant azo dyestuffs. 


PicraMic acid coupled in alk. soln. with 8-ethoxy 1-NAPHTHOL 5-sulfo. A GREEN acid mor- 
dant (Cr) or developed (CrO,) dye, fast to milling and light. 


1,157,169—Oct. 19, 1915. Charles MetriEeR, Switzerland. (Geigy.) 
Mordant-dyeing azo dye. 


2-Chlor 5-amino BENZOIC acid coupled with saLicyiic acid, pptd. by salt, filt., pressed, and 
press-cake heated in autoclave at 150° with strong NaOH and copper powder. Green-yELLOW 
acid and developed (CrO,) dye, which when chromed is fast to light, potting and milling. 


1,157,525—Oct. 19, 1915. Albert E. Grsster, New York. 
Manufacture of color-lakes. 


DiIANnIsIDIN coupled with 2 mols. 2-NAPHTHOL 6-sulfo or other, pptd. as lake by water sol. 
salt of metal such as Ba, Ca, Al, Cu, etc., especially copper. Buus lakes, fast to water, oil, 
benzene and varnish and will not sublime. } 


1,159,375—Nov. 9, 1915. Oscar GUNTHER, Germany. (Synthetic.) 
Azo dye. 


ANTHRANILIC acid or other, coupled with 2-AMINO 5-NAPHTHOL 7-sulfo, or other, in acid 
soln., then combined with diazo 4-nitro 2-amino PHENOL. Rep to BLACK acid and developed 
(CrO,) dyes, which when chromed are fast to alks., acids, light, milling and potting. 


1,159,3S86—Nov. 9, 1915. Johann Huismann, Germany. (Synthetic.) 


Yellow azo dye. 


Dehydro thio ToLumpIN mixed with dil. H,SO, and evaporated to dryness, residue heated 
in oil bath to 235-250° in vacuum, till aq. ceases to condense, and resulting mono sulfo comp. 


GROUP VI.—AZO 177 


heated at 80-90° in large amount of fuming H,SO,, diazotized and coupled with aceto ACETANILID 
or other. Yellow direct dye, fast to light. 


1,160,406—Nov. 16, 1915. Martin Hrerzperc, Germany. (Synthetic.) 
Azo dye. 
DIANIsiIpIN coupled in alk. soln. with r mol. each of 3-amino phenyl 1.2-NAPHTHIMIDAZOLE 


s-oxy 7-sulfo and 2-AMINO 5-NAPHTHOL 7-Sulfo. Other components claimed. Rep, vioLET and 
BLUE direct and developed dyes, fast to washing when treated with formaldehyde. 


1,160,471—Nov. 16, 1915. Hermann WacGNER and Josef Ersrer, Germany. (Héchst.) 
Yellow dyestuffs and process of making same. 


Diamino TRIPHENYLMETHANE, or other, diazotized and coupled with 2-chlor phenyl methyl 
PYRAZOLONE, or other. YELLOW direct dye that is fast to milling, light, and sulfur and is suit- 
able for lakes. 


1,166,346—Dec. 28, 1915. Hugo GELDERMANN and Ferdinand Haas, Germany. (Berlin.) 
Yellow disazo dyes. 


2-Amino DIPHENYL ether sulfo acid, 2 mols., coupled in alk. soln. with 4.4’-dipyrazolone 
3.3’-DITOLYL methane from 4.4’-dihydrazin 3.3’-pIToLyL methane and aceto ACETIC ester combined 
to dipyrazolone. Other components claimed. YrEnLow acid dye, fast to washing. 


1,169,329—Jan. 25, 1916. Matthias Latren, Germany. (Synthetic.) 
Blue-violet azo dye. 


I.5-NAPHTHALENE DIAMIN 3.7-disulfo coupled in neutral-or acetic soln. with 2 mols. cRE- 
SIDIN, retetrazotized and coupled with 2 mols RESORCIN. Vu1oLET direct and developed dyes, fast 
to washing when treated with formaldehyde. 


1,169,344—Jan. 25, 1916. 
Wilhelm NEELMEIER, Heinrich JorpAN and Karl Hreusner, Germany. (Synthetic.) 
Blue disazo dye. 


s5-Amino 4-chlor acetyl 2-amino PHENOL, methyl ether, coupled in acetic soln. with the ethyl 
ester of I-AMINO 2-NAPHTHOL 6-sulfo, rediazotized and coupled with 1-NAPHTHOL 4-sulfo, then 
saponified. Other components claimed. Buus direct and developed dyes, which when coupled 
on fiber with beta naphthol or other, are fast to washing and give white discharge. 


1,172,061—Feb. 15, 1916. Rudolf ScHuLe, Germany. (Cassella, N. Y.) 
Fast yellow dyes and process of making same. 


Diamino TRIPHENYL METHANE or other, coupled in alk. soln. with 2 mols. 2’-chlor 4’-sulfo 
phenyl methyl pyrRAZzOLONE, or other. Orange-yELLow direct or acid fast dyes. 


1,173,077—Feb. 22, 1916. Fritz ACKERMANN, Germany. (Berlin.) 
Disazo dye. 


4.4’-Diamino DIPHENYL urea coupled in acetic soln. with 2-AMINO 8-NAPHTHOL 6-sulfo, then 
in alk. soln. with rEsorcIN. Red-srown direct and developed dyes, fast to washing when 
treated with formaldehyde, or other. 


1,180,885—Apr. 25, 1916. Jens DepicHeN and Werner Lancr, Germany. (Berlin.) 
Blue tetrakisazo dyes. 


2-NAPHTHYLAMIN 4.8-disulfo coupled in acid soln. with I-NAPHTHYLAMIN, again coupled in 
acetic soln. with I-NAPHTHYLAMIN 6-sulfo, again diazotized and coupled with 4-xyLip1n, di- 
azotized a fourth time and coupled with rEsorcin, Other components claimed. BuriueE direct 
and developed dyes, fast to light and washing when treated with formaldehyde. 


1,183,378—May 16, 1916. Carl HzInpericH, Germany. (Synthetic.) 
Azo dye and process of dyeing. 


2-Nitro 4-TOLUIDIN, 2 mols., coupled in alk. soln. with one mol. bis. — (4/-oxy 2/-naph- 
thoyl) (2) 3-TOLUYLENE DIAMIN 5-sulfo. Process for application to fiber and other components 
claimed. Vari-coLoRED direct and developed dyes, fast to washing and boiling. 


178 DIGEST OF PATENTS 


1,183,831—May 16, 1916. Jens DepicHEN and Werner Lancer, Germany, (Berlin.) 
Green substantive trisazo dyes. 

2-NAPHTHYLAMIN 4.8-disulfo coupled with I-NAPHTHYLAMIN, recoupled in alk. soln. with 
3/-amino benzoyl 1-AMINO 8-NAPHTHOL, 4-sulfo, again coupled in alk. soln. with phenyl methyl 
PYRAZOLONE. Other components claimed. A GREEN direct dye. 


1,183,413—May 30, 1916. Herbert LEVINSTEIN and James BappiLty, England. (Levinstein.) 
Production of fast orange, red or brown shades on vegetable fibers and 
dyestuffs therefor. 


3/-Nitro benzoyl 3-PHENYLENE DIAMIN coupled in alk. soln. with 3’-amino benzoyl 2-AmMINo 
5-NAPHTHOL 7-Sulfo, reduced with Na,S, rediazotized and coupled with 2 mols. REsorcin. Other 
components claimed. ORANGE, RED and BRowN direct and developed dyes, fast fo light, alks., 
strong HNO,, and fast to washing after formaldehyde treatment. 


1,188,421—June 27, 1916. Heinz E1cHwrpg, Germany. (HoOchst.) 
Blue monoazo dyes and process of making same. ; 

I-AMINO 8-NAPHTHOL 4-Sulfo, or other, coupled in alk. or neutral soln. with phenyl I- 
NAPHTHYLAMIN 8-sulfo. Buiue acid or direct dyes, fast to washing, milling, rubbing and light. 


1,186,545—June 27, 1916. Paul Jutius and Ernst FussENEGGER, Germany. (Badische.) 
Azo dyes. 

2'-Chlor benzoyl 1-AMINO 7-NAPHTHOL, or other, free from salt forming groups coupled with 
2-NITRANILIN. Other components claimed. Rep to BLuE developed dyes suitable for lakes, fast 
to water, washing, light and Cl. 


1,193,829—Aug. 8, 1916. Rudolf ScuHu.tst, Germany. (Cassella, Nox) 
Disazo-dyestufis and process of making the same. 

METANILIc acid azo I-NAPHTHYLAMIN coupled in alc. soln. with 3’-amino phenyl 8-oxy. 1.2- 
NAPHTHIMIDAZOLE 6-sulfo. Other components claimed. Products are diazotized on fiber and 
coupled with phenyl methyl pyRazoLONE, or derivs. GREEN developed dyes, fast to washing, 
soap and light. 2 


1,197,633—Sept. 12, 1916. Erwin Horra, Germany. (Hdéchst.) 
Process of producing yellow insoluble azo dyes on the fiber. 

4-Nitro 2-amino BENzoIC acid ester coupled with 2-NAPHTHOL on the fiber either as dye 
or printing comp. YELLow developed dyes for printing, fast to washing, Cl and chlorate, and 
discharge white. 


1,199,233—Sept. 26, 1916. Michael Bornicer, Switzerland. (Sandoz.) 
Manufacture of chromable secondary o-oxy disazo dyestufis. (Products also 
claimed.) 


Picramic acid, or 4-chlor 2-amino phenol 6-sulfo acid, etce., coupled with 1-AMINO 8-NAPH- 
THOL 3.6-disulfo in alk. soln., recoupled in alk. soln. with 4’-sulfo phenyl methyl PyRAZOLONE. 
Other components claimed. Buack or RED and GREEN acid and developed (CrO,) dyes, which 
when chromed are fast to washing, potting and light. 


1,199,234—Sept. 26, 1916. Melchior BornicER, Switzerland. (Sandoz.) 
Manufacture of chromable secondary disazo dyestuffs. (Products also claimed.) 

PicraAMiIc acid, 2-amino 6-nitro phenol 4-sulfo acid, or other, coupled in alk. soln. with 
2-AMINO 8-NAPHTHOL 6-sulfo, and recoupled with 4’-sulfo phenyl methyl pyrazotone. Other 
components claimed. Red-srown acid and developed (CrO,) dyes, which when chromed are 
fast to milling, potting and light. 


1,199,890—Oct. 3, 1916. Peter HauptMann, Germany. (Synthetic.) 
Wool-dye. 


as-Ethyl benzoyl (2)4-ToLUYLENE DIAMIN, or other, coupled with 1-NAPHTHOL 4-sulfo, or 
other. Rep to YELLOW to BROWN acid dyes, fast to fulling. 


1,201,544—Oct. 17, 1916. Wilhelm Bercpoit, Germany. (Synthetic.) 
Red wool-dye. 


Acetyl 3-PHENYLENE DIAMIN 4-Sulfo with sulfo group ortho to unsubstituted NH,, or other, 
coupled with 2-AMINO 8-NAPHTHOL 6-sulfo. Rep acid dye, fast to light. 


GROUP VI.—AZO 179 


1,206,232—Nov. 28, 1916. August IL, Lasxa, Germany. (Griesheim.) 
Azo-dyestuffs and process of producing the same. 
as-Dimethyl 4-PHENYLENE DIAMIN azO ANILIN coupled with 2-oxy 3-NAPHTHOIC acid anilid. 


Other components claimed. Processes for dyeing and printing described. Briacx developed 
dye, suitable for printing. 


-1,209,154—Dec. 19, 1916. Rudolf Haucwitz, Germany. (Berlin.) 
Trisazo dyes. 

4-NITRANILIN azo 4-methoxy 3-roLUuIpIN reduced, tetrazotized and coupled with 1 mol. each 
of 1.8-dioxy NAPHTHALENE 3.6-disulfo and 3-PHENYLENE DIAMIN. Other components claimed. 
VioLeET and sBLAcK direct and developed dyes, which when developed with diazo 4-nitranilin 
give black color. 


1,210,751—Jan. 2, 1917. 
Eugen ANDERWERT, Hermann Fritzscue and Heinrich ScHosBeL, Switzerland. (Basle.) 
Substantive orthooxyazo dyestuffs and a process of making same. 
2.2/-Dioxy BENZIDIN (by saponifying dianisidin with AICl,) coupled with 2-aAMINO 2-NAPH- 
tHOoL sulfo or disulfo (2.5.1.7.). Other components claimed. Vari-coLorEp direct dyes. 


1,210,808—Jan. 2, 1917. Carl JAGERSPACHER, Switzerland. (Basle.) 
Orange to red dyestuffs able to be chromated and a process of making same. 
2-amino PHENOL 4-sulfo coupled with nitro oxy phenyl methyl pyrazotone. Other com- 


ponents claimed. Vari-coLorep developed (CrO,) or acid mordant (Cr) dyes, which when 
chromed are fast to fulling, potting, and light. 


1,213,075—Jan. 16, 1917. 
Albert Ciaustus, Bernhard ScHONER and Otto Sresert, Germany. (Berlin.) 
Disazo dyes. 
4-Nitro 2-amino PHENOL, or other, coupled in alk. soln. with 2-AMINO 5-NAPHTHOL 7-sulfo, 
recoupled in alk. soln. with ethyl 4’-sulfo benzyl ANILIN, or other. VuioLter and sLacxk acid 
and developed (CrO,) dyes, which when chromed are fast to light, washing and milling. 


1,215,359—Feb. 13, 1917. Joseph FLACHSLAENDER and Paul G. List, Germany. (Synthetic.) 
Dyes and process of dyeing. 
4-Nitro 2-ToLUIDIN, or other, coupled with tetrahydro-naphthalid of 2-oxy 3-NAPHTHOIC acid. 


Process for production on fiber described. Vari-coLtorEep developed and direct dyes, fast to 
boiling, Cl and washing. 


1,216,760—Feb. 20, 1917. 
Berthold Wutu, Bertram Mayer, Carl JacerspacHER and Eugen ANDERWERT, 
Switzerland. (Basle.) 

Copper compounds of orthoozyazo dyestuffs and a process of making same. 

2-amino PHENOL 4-sulfo, or other, coupled with 2-AMINO 5-NAPHTHOL 7-sulfo, or other, then 
boiled in aq. soln. with soluble copper salt to form a soluble copper dye compound. Vart- 
COLORED acid dyes, fast to washing, light and copper, and suitable for lakes. 

Note 1,216,812 and 13, 1,233,433, 1,234,994 and 1,242,536. 


1,216,812—Feb. 20, 1917. Carl JacERSPACHER and Berthold Wutu, Switzerland. (Basle.) 


Copper compounds of orthooxyazo dyestuffs and a process of making 

same. 

2-amino PHENOL, 4-Sulfo, or other, coupled with aceto ACETANILID, or other, and heated with 
soln. of copper sulfate to form soluble dye compound. YELLow, BRowN and ORANGE acid and 
acid mordant (Cu) dyes, fast to washing and light. 

Addition to 1,216,760. 


1,216,813—Feb. 20, 1917. Carl JAGERSPACHER, Switzerland. (Basle.) 


Metal compounds of orthooxyazo dyestuffs and a process of making same. 


4-Nitro 2-amino PHENOL, or other, coupled with pYRAZOLONE, or other, then heated in soln. 
with copper comp., CrF., or other, to form solube metal dye comp. Vari-coLorEpD acid and 


180 DIGEST OF PATENTS 


acid mordant (Cr, Cu) dyes, fast to washing and light, which when twice chromed are fast to 
fulling, potting, etc. 
Addition to 1,216,760. 


1,217,042—Feb. 20, 1917, Carl MrNscHiNG, England. (Mounsey.) 
Monoazo dyes. (Process also claimed.) 

Picramic acid coupled in acetic soln. with 2-NAPHTHYLAMIN, or other, to produce dye with 
azo and amino groups in ortho position to each other. GREEN acid mordant (meta chrome) 
dyes, fast to milling and light. 


1,219,954—Mar. 20, 1017. 
Richard KircHuorr, Jens DEDICHEN and Werner LancrE, Germany. (Berlin.) 
Ortho-oxy-monoazo dyes. 
Picramic acid coupled in alk. soln. with acetyl 4-amino PHENOL, or other. Brown GREEN 
acid mordant (Cr) dyes, fast to washing, milling, potting and light. 


1,221,849—Apr. 10, 1917. 
Gadient Enc1, Fritz Srraus, and Armin Gros, Switzerland. (Basle.) 

Chromium compounds of azo dyestuffs containing groups able tw be chro- 

mated and a process of making the same, 

4-Chlor 2-amino PHENOL azo 2-carbo BENZOYL acetic acid, or other, heated as paste and in 
alk. aq. soln. with chromium hydroxide to form solube chromium comp. VARI-COLORED acid 
mordant (Cr) dyes, fast to washing, light, alk. and potting. 

Note 1,216,760, 1,216,812 and 13. 


1,232,056—July 3, 1917. Herbert LEvinstr1n and James Bappitty, England. (Levinstein.) 
Production of fast shades on vegetable fibers and dyestuffs therefor. 

3-3/-Diamino azoxy TOLUENE, coupled in alk. soln. with 3-amino phenyl 1.2-NAPHTHIMI- 
DAZOL 5-oxy 7-sulfo, tetrazotized and coupled with 2 mols. RESORCIN. Orange-RED direct and 
developed dyes, fast to soap after treatment with formaldehyde. 


1,233,433—July 17, 1917. Berthold Wut and Carl JacERspacHER, Switzerland. (Basle.) 

Copper compounds of orthooxyazo dyestuffs and a process of making same. 
I-AMINO 2-NAPHTHOL 4-sulfo coupled in alk. soln. with peri-NAPHTHINDANDIONE, then heated 

in aq. soln. with copper sulfate or other to form soluble metallic dye compound. Other com- 

ponents claimed. Vari-coLoRED acid mordant (Cu) dyes, fast to washing, alkali and light. 
Addition to 1,216,760. 


1,233,742—July 17, 1917. Eugen ANDERWERT and Heinrich ScHopeEL, Switzerland. (Basle.) 
Wool disazo dyestuffs and a process of making same. 

3.3’-Diamino 4.4’-dimethyl pIPHENYL methane, coupled with 2 mols. 1-NAPHTHOL 4-sulfo or 
1 mol. of this and 1 mol. of 2-NAPHTHOL, or other. Orange-rED acid dyes, fast to washing, 
light and fulling. 


1,234,994—July 31, 1917. Berthold WurxH and Carl JacERSPACHER, Switzerland. (Basle.) 
Copper compounds of orthooxyazo dyestufis and a process of making same, 
4-Sulfo 2-amino saLicyLic acid coupled with 2-carbo BENZOYL acetic acid, then heated in 
aq. soln. with soluble copper salt to form soluble copper dye. Other components claimed, 
GREEN, BLUE to VIOLET acid mordant dyes, fast to washing and light. 
Addition to 1,216,760. 


1,235,253—July 31, 1917. James H. StrEpsins, Jr., New York. 
Dyestuffs. (Process also claimed.) 

4-NITRANILIN coupled in acid soln. with 1.8-dioxy NAPHTHALENE 3.6-disulfo then combined 
in alk. soln. with one equivalent of tetrazo BENzIDIN and finally coupled with 1-NAPHTHOL 5- 
sulfo. Other components claimed. BLur, BLACK and BRowN direct and acid dyes. 


ee =a a ae 


GROUPIVI.—470 I81 


1,237,183—Aug. 14, 1917. Gadient Ener and Carl JacENSPACHER, Switzerland. (Basle.) 
Process for the manufacture of copper compounds of orthooxyazo dyestuffs. 
Improved copper compounds of ortho oxy azo dyes. 
I-NAPHTHOL 5-sulfo mixed in alk. carb. soln. with CuSO, and allowed to flow into soln. 
of diazo 1-AMINO 2-NAPHTHOL 4-sulfo. Compounds with other ortho oxy azo dyes claimed. 
ViI0LET acid dyes, fast to light, washing and alks. 


Note 1,216,760 and 1,216,812 (Wuth and Jagerspacher) in which copper salt is added after 
dye has been coupled. 


1,237,192—Aug. 14, 1917. Fritz Funckre and Carl JAGERSPACHER, Switzerland. (Basle.) 
Leucotriarylmethanazo dyestuffs and a process of making same. 

Amino leuco PATENT BLUE, derived by nitrating and reducing leuco Patent Blue, diazotized 
and coupled with 2-NAPHTHOL, a pyrazolone, or other. BLur and GREEN acid mordant and devel- 


oped (Cu, CrO,) dyes, which when chromed or coppered are fast to washing and light. 
Note 1,237,103, which gives a copper compound of above. 


1,237,193—Aug. 14, 1917 Fritz Funcke and Carl JAGERSPACHER, Switzerland. (Basle.) 
Copper compounds of leucotriarylmethanazo dyestuffs and a process of 

making same. Copper compound of No. 1,237,192. 

Amino leuco PATENT BLUE azO 2-NAPHTHOL, treated in hot aq. soln. with soluble copper 
salt, to form soluble copper dye compound. BLueE to GREEN acid mordant dyes, fast to light and 
washing. 

Addition to 1,237,192. 


1,241,153—Sept. 25, 1917. Rudolf Scuu.r, Germany, 
Disazo dyestuff and process of making same. 

4-NITRANILIN coupled in HCl soln. with cresip1n* and recoupled in alk. soln. with 3’- 
amino phenyl 8-oxy 3.6-disulfo 1.2-NAPHTHIMIDAZOLE. Coupled on fiber with phenyl methyl 
pyrazolone or other, or developed with diazo 4-NITRANILIN the black dye becomes green. BLack 
and GREEN direct and developed dyes, which when developed are fast to washing, soap and light. 

* Compound is called in patent “Amino cresol methyl ether.”” Above patent contains spe- 
cific while 1,193,829 gives generic claims. 


1,265,031—May 7, 1918. 
Eugen ANDERWERT, Herman Fritzscue and Heinrich ScHoset, Switzerland. (Basle.) 

Substantive orthooxyazo dyestuffs and a process of making same. 

2-Amino PHENOL sulfo, or other, diazotized and coupled with I-NAPHTHYLAMIN, again di- 
azotized and coupled with 3-amino benzoyl 2-AMINO 5-NAPHTHOL 7-Sulfo. Lists of components 
are given, some form of 2-amino 5-naphthol 7-sulfo always being used as third coupling agent, 
Buve direct dyes, adapted for lakes. 

Addition to 1,263,030. 


1,270,290—June 25, 1918. Carl HaceMann, Germany. (Synthetic.) 
Gray azo dyes. 

4.5-Dichlor ANILIN 2-sulfo coupled in acid soln. with 1-NAPHTHYLAMIN 6-sulfo, rccoupled in 
acid soln. with 1-NAPHTHYLAMIN 7-sulfo, again coupled in alk. soln. with 2-AMINO 8-NAPHTHOL 
6-sulfo. Other components claimed. Gray direct dyes, fast to light. 

Note that by manner of coupling the amino groups of both middle components are in same 
nucleus. 


1,281,243—Oct. 8, 1918. Ernest F. EHRHARDT and Herbert W. Ruruarpt, England. 
Azo dye and process of making. 

Picramic acid coupled with commercial crEsoL (60 per cent meta, 40 per cent para) using 
only sufficient diazo comp. to combine with meta comp., the Meta Chrome Brown Y filt. off, 
then more diazo comp. added to combine with the para cresol. The first azo product can be 
more completely separated as dye acid. Isolated 4-cresol also claimed. Brown acid mordant 
dye, fast to milling, scouring and light. 


182 DIGEST OF PATENTS 


1,270,325—June 25, 1918. Emil Reser, Switzerland. (Basle.) 
Monoazo dyestufis of the pyrazolone series able to be chromated and 
process of making same. 


ANTHRANILIC acid coupled in alk. soln. with 2-oxy 5/-sulfo 3’-carbo phenyl methyl Pyrazo- 
LONE, prepared by condensing aceto ACETIC ester with 2-oxy 5-sulfo 3-carbo PHENYL hydrazin. 
Other components claimed. YELLOW to ORANGE acid developed (CrO,) dyes, which when 
chromed are fast to fulling and potting. 

Addition to 1,210,808. 


1,242,536—Oct. 9, 1917. Gadient Ener and Carl JacERSPACHER, Switzerland. (Basle.) 
Chromium compound of azo dyestuffs and a process of making same. Chro- 
mium compounds of azo dyes having ortho oxy groups. 


4-Nitro 2-amino PHENOL, 2-amino phenol 4-sulfo, or other, heated in aq. with sod. acetate 
and CrF,, then diazotized and coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo, or other, and 
boiled in aq. with CrF,,. GREEN and vIOLET acid mordant dyes, fast to alks., light, fulling, 
potting, washing and chromating. 

Note 1,216,760 and 1,259,499 for dyes partly substituted by Cr. 


1,259,499—Mar. 10, 1918. Gadient Enc1 and Carl JacErspacHER, Switzerland. (Basle.) 
Chromium compounds of azodyestuffs and process of making same. Azo dyes 
having ortho oxy groups partly substituted by Cr. 


4-Nitro 2-amino PHENOL heated in aq. with sod. acetate and CrF,, or other, product di- 
azotized and coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo, or other. 
Above was original patent and 1,242,536 should have followed as an addition. 


1,264,604—Apr. 30, 1918. Rene Boon and Paul Nawiasxy, Germany. (Badische.) 
Chromium compounds of azo dyes. (Process also claimed.) Soluble chromium com- 
pounds of azo dyes. 
ToLvIpIN 2.2/-disulfo disazo saLicyLic acid, or other, boiled in aq. with CrF, and Cr for- 
mate, or other. Binder for liberated mineral acids must be added. Dye fixed with alkali after 
printing. YELLOW, RED and BRowNn acid mordant dyes, suitable for printing. 


1,265,030—May 7, 10918. 
Eugen AnpDERWERT, Hermann FritzscHe and Heinrich ScuoseE., Switzerland. (Basle.) 

Substantive orthooxyazo dyestuffs and a process of making same. Ortho oxy 

azo dyestuffs. 

5-Nitro 2-amino PHENOL, or other, coupled with 2-AMINO 5-NAPHTHOL 7-sulfo, diazotized 
again and coupled with 1-AMINO 8-NAPHTHOL 3.6-disulfo. Several complex amino oxy sulfo 
comps. for middle components are given... Violet-sLu® direct dyes. 

Note 1,265,031. 


1,281,938—Oct. 15, 1918. Albert E. Gesster, New York. 
Disazo coloring-matters and process of making the same. 


Totip1In coupled with 2 mols. 2-NAPHTHOL 6- or 7-sulfo in NH, soln. and alkali or metallic 
salt formed. Rep lakes, (Cu. etc.), fast to aq. oil and organic solvents. 
Near S. 366—‘“Diamin Red B.”’ Note that patent calls first component di-p-amino-ditolyl. 


1,282,354—Oct. 22, 1918. ‘ 
Eugen ANDERWERT, Hermann Fritzscue and Heinrich ScuoseE., Switzerland. (Basle.) 
4-Nitro 2-amino PHENOL, coupled in alk. soln. with 3’-amino benzoyl 2-AMINO ‘5-NAPHTHOL 
7-sulfo or disulfo (2.5.1.7). Other components claimed. Rep, VIOLET, etc., direct dyes, suitable 
for lakes. 
Note 1,282,355 and 56. 


1,282,355—Oct. 22, 1918. 
Eugen AnpERWERT, Hermann Fritzscue and Heinrich Scnose, Switzerland. (Basle.) 
Substantive orthooxyazo dyestuffs and process of making same. 

BENz1IDIN coupled with one mol. saLicyLic acid and in weak acid soln. with 2-amINo 5- 
NAPHTHOL 7-sulfo, then in alk. soln. combined with diazo 2-amino sulfo saticynic acid. Other 
components claimed. VarI-coLorED direct dyes, suitable for lakes. 

Addition to 1,282,354. 


GROUP VI.—AZO . 183 


1,282,356—Oct. 22, 1918. 
Eugen ANDERWERT, Hermann FritzscHeE and Heinrich Scuoset, Switzerland. (Basle.) 
Substantive orthooxyazo dyestuffs and process of making same. 
2-amino PHENOL coupled in alk. soln. with 5.5’-dioxy 7.7’-disulfo 2-DINAPHTHYL urea com- 
bined with one equivalent of tetrazo DIANISIDIN and finally coupled with 1-NAPHTHOL 4-sulfo. 


Other components claimed. BLueE, vIoLET, etc. direct dyes, suitable for lakes. 
Addition to 1,282,354. 


1,283,231—Oct. 29, 1918. Herbert L&eviInsteIn, England. 
Production of azo dyestuffs. (Product, not process, claimed.) 


4-Amino ACETANILID or derivs., coupled with 2-oxy 3-NAPHTHOIC acid, then hydrolyzed. 
Buiue acid mordant dyes that may be dyed by one-bath method, and are fast. 


_1,286,411—Dec. 3, 10918. Emil Reser, Switzerland. (Basle.) 
Dyestuff of the pyrazolone series and process of making same. 

ANILIN, 3-amino benzoic acid, or other aryl amin, coupled in alk. soln. with 5’-sulfo 3’- 
carbo 2’-oxy phenyl methyl PyrazoLoNne or other aryl substituted pyrazolone with oxy and car- 
boxy groups in the aryl radical. Green-yELLOW to RED acid, acid mordant (Cr) or developed 


(CrO,) dyes, which when chromated are fast and suited for ene on Cr mordant. 
Note 1,210,808 and 1,270,325. 


1,292,385—Jan. 21, 1919. 
Eugen ANDERWERT, Hermann FritzscueE and Heinrich Scuoser, Switzerland. (Basle.) 

Copper compound of substantive orthooxyazo dyestuff and process of 

making same, 

2-Amino 4-nitro PHENOL azo 3’-amino benzoyl 2-amino 5-NAPHTHOL 7-sulfo, mixed in large 
volume dil. HCl at 50°, sufficient CuSO, added and temp. raised to 80-90° and almost neut. 
with Na, CO,. Large number of other ortho oxy azo dyes are tabulated and claimed. Vart1- 
COLORED Peet dyes, fast to light, washing, alk. and acid. 

Note 1,210,751. 


1,310,532—July 22, 19109. Whitney B. Jones, New Jersey. (Butterworth.) 
Brown dyestuff. 


Picramic acid coupled with 1-NAPHTHYLAMIN or with Cleve’s acid, in acetic soln., redi- 
azotized and coupled with saticyitic acid. Fast BRowN direct dyes. 


1,314,921—Sept. 2, 1910. Chester E. AnpREws, Pennsylvania. (Selden.) 
Cymene dyestuff and process of making same. (Process not claimed.) 

Pure or crude 2 or 3 amino CYMENE (4-iso propyl TOLUENE) coupled with 2-NAPHTHOL or 
other oxy aromatic comps., in soln. or on prepared fiber. Red-ORANGE or VARI-COLORED acid, 


acid mordant or developed dyes, of greater tinctorial power than those made with other first 
components than cymene derivs. 


1,314,922—Sept. 2, 1919. Chester EK. AnpREws, Pennsylvania. (Selden.) 
Cymene dye. P 

2 or 3-Amino cCYMENE coupled with ToLUYLENE DIAMIN or other alphylamin or deriv., at 
least one sulfo group being present in a naphthalene nucleus. Vari-coLorED acid, direct or 


basic, etc. dyes of greater coloring power than prior patents of analogous procedure. 
Note 1,314,921. 


1,314,925—Sept. 2, 1919. | Chester E. Anprews, Pennsylvania. (Selden.) 
Dimethyl-diisopropyl-benzidin azo dyestuffs and process of making same. 

(Process not claimed.) 

Diisopropyl toLtipin (di-cymidin), coupled with 2 mols. NAPHTHIONIC acid, or other aro- 
matic amin, or derivs. VARI-COLORED direct or basic dyes. 

Note 1,314,921-2. 


1,314,926=Sept. 2, 1919. Chester E. Anprews, Pennsylvania. (Selden.) 


Dimethyl-diisopropyl-benzidin azo dyes and process of making same. 
(Process not claimed.) © 


184 DIGEST OF PATENTS 


Diisopropyl toL1pIN is coupled with 2 mols. of saLicy.Lic acid, or other oxy aromatic comp., 
or with 1 mol. each of two different oxy comps. VaRi-coLoRED acid or acid mordant dyes. 
Addition to 1,314,925. 


1,316,781—Sept. 23, 1910. Hermann FritzscuHe, Switzerland. (Basle.) 
Azo dyestufis dyeing mordanted goods. 


2-Amino PHENOL 4-sulfanilid, or other amino ortho oxy aryl sulfo aryl amids, coupled with 
1.8-dioxy NAPHTHALENE 3.6-disulfo, or other, in presence of Ca(OH), to neut. acid, then excess 
Na,CO, added, filt., and salted out. Rep or siue acid, acid mordant or developed (CrO,) dyes, 
which when chromated are fast to washing, fulling, potting and light. 


1,319,852—Oct. 28, 1919. Jens Depicuen, Germany. (Chem. Found.) 
Blue tetrakisazo dyes. 


METANILIC acid or deriv., coupled with 1-NAPHTHYLAMIN, rediazotized and coupled in acetic 
soln. with 1I-NAPHTHYLAMIN 6-sulfo, the second and third components being derivs. of the 
naphthalene series, again coupled in alk. soln. with 2-amino 5-NAPHTHOL 7-sulfo and finally 
coupled with rEsorcIN. Buus direct and developed dyes, which when developed on fiber by 
formaldehyde are fast to light and washing. 


1,323,285—Dec. 2, 1910. Carl JAGERSPACHER, Switzerland. (Basle.) 
Azo dyestuffs dyeing on mordants and process of making same. 

ANTHRANILIC acid or other amindg comp. that has no hydroxyl group in ortho position, 
coupled in acetic acid soln. with 1.8-dioxy NAPHTHALENE 3-sulfo 6-carbo acid, or derivs. Rep 
to BLUE to BLACK acid or developed (CrO,) dyes, suitable for printing blue to black on chrom- 
ium mordant. 


1,325,841—Dec. 23, 19109. Hermann FRrRitzscHet, Switzerland. (Basle.) 
Azodyestufis dyeing mordanted goods. 

2-Amino PHENOL 4-sulfamid, coupled in alk. soln. with 2-NAPHTHOL 6-sulfo or the imid is 
coupled with 2 mols. of 2-NAPHtTHOL. Derivs. are claimed. REp to VIOLET to BLUE or BLACK 
acid, acid mordant (Cr, Cu) or developed (Cu, CrO,) dyes, fast to washing, fulling, potting 
and light when chromated. 

Note 1,316,781. 


1,327,688—Jan. 13, 1920. Richard Taccrset,, New York. (National.) 

Azo dyes and process of making same. 3 
(2)3-TOLUYLENE DIAMIN tetrazotized and coupled with 1 mol. of same or of the sulfo deriv. 

of (4)3-TOLUYLENE DIAMIN and with an unsulfonated comp. such as 3-PHENYLENE DIAMIN. 


Orange-BROWN to red-BROWN direct or developed dyes that may be coupled on fiber with diazo 
comps. such as 4-nitranilin and are then fast to washing. 


1,338,397—Apr. 27, 1920. Emil Reser, Switzerland. (Basle.) 
Disazodyestufis able to be chromated. 


2-TOLUIDIN azo 2-TOLUIDIN coupled in alk. soln. with 5’-sulfo 3’-carbo 2/-oxy phenyl methyl 
PYRAZOLONE. First and second components may be any diazotizable amin and the third an 
oxy carboxyl aryl pyrazolone. Rep to ORANGE direct, acid mordant (Cr) and developed (CrO,) 
dyes, fast to fulling and potting when chromated, of little change in shade owing to OH and 
COOH group being in nucleus different from chromophore carriers. 


1,338,414—Apr. 27, 1920. Eugen ANDERWERT and Hermann FRritzscHE, Switzerland. (Basle.) 
Substantive orthooxyazodyestuffs. 


2-Amino 6-nitro PHENOL 4-sulfonamid coupled in alk. soln. with phenyl 2-aMINO 3-NAPHTHOL 
7-sulfo or derivs. Other ortho oxy amino aryl sulfonamids are claimed. Rep to vioxeT direct, 
acid mordant and developed (Cr) dyes, which when coppered are fast to acid, alk. and light. 


1,338,506—Apr. 27, 1920. Carl JAcERSPACHER and Max Ister, Switzerland. (Basle.) 
Disazodyestuffis dyeing mordanted fibers. ; 
ANTHRANILIC acid, or other amino carbo acid, condensed in NaOH soln. with one mol. 


FORMALDEHYDE bisulfite by heating at 40-50° and resulting N-methylene sulfo comp. added to 
diazo 3-amino BENzoIc acid in sod. acetate soln., separated dye boiled in 2 per cent NaOH to 


¥ 
‘ 


GROUP VI.—AZO 185 


split off N-methylene sulfo group and separated 4-amino azo BENZENE 3.3/-dicarbo acid coupled 
with 2’-carbo phenyl methyl pyrazoLoneE in alk. soln. YELLOW to ORANGE to BROWN acid, acid 
mordant (Cr) or developed (CrO,) dyes, fast when chromated, useful for printing with Cr 
mordant. 


1,342,134—June 1, 1920. Arnold ScHEpLER, England. (Basle.) 
Dyestuffs capable of being diazotized and process of making same. 


3.3'/-Diamino 4.4/-DITOLYL methane or deriv., coupled in alk. soln. with 2 mols. 3’-amino 
benzoyl 2-AMINO 5-NAPHTHOL 7-sulfo or other deriv. with free diazotizable amino group, which 
when diazotized on fiber and coupled with 2-NaPHTHOL or other non-sulfo comp., forms orange- 
RED to blue-vioLET developed dyes of pure, tone, fast to washing. 


1,359,969—Nov. 23, 1920. Guillaume de Montrmo.uin, Switzerland. (Basle.) 
Acid wool dyestuffs. 


4-PHENYLENE DIAMIN 4/-tolyl sulfone acetylated in alc. soln., then diazotized and coupled 
in acetic soln. with 2-aAMINO 8-NAPHTHOL 6-sulfo, or deriv. Orange-rED to dark vioLET acid 
dyes, fast to washing and light. 


1,362,936—Dec. 21, 1920. Hermann FRritzscHer, Switzerland. (Basle.) 
Diazotizable dyestuffs easily soluble in water. 


2-NAPHTHYLAMIN azo 3/-amino benzoyl 2-AMINO 5-NAPHTHOL 7-sulfo, boiled in aq. with 
FORMALDEHYDE and sod. bisulfite, and the N-methyl w-sulfonate separated. Or 3/-amino ben- 
zoyl 3-PHENYLENE DIAMIN coupled with 2 mols. of 3-phenyl PyRAZOLONE carbo acid and similarly 
treated with formaldehyde bisulfite. Similar components claimed. YELLOW, ORANGE to violet 
RED direct and developed dyes that may be diazotized on fiber and coupled with 2-NAPHTHOL. 


1,363,886—Dec. 28, 1920. 
Thomas H. Leamine and Theresa M. Susemiuit, New York. (National.) 
Disazo dye. 


Acet 4-PHENYLENE DIAMIN of 4-nitranilin, or other, coupled with 1-amino 8-NAPHTHOL 4- 
sulfo in acetic soln., product separated and coupled in alk. carb. soln. with diazo acet. 4- 
PHENYLENE DIAMIN, saponified or reduced and separated as HCl salt. Rep to green-BLAcK 
direct and developed dyes that can be diazotized on fiber and coupled with 2-NAPHTHOL, or 
other. 


1,365,040—Jan. 11, 1921. Thomas H. Letaminc, New York. (National.) 
Disazo dye. 


4-NITRANILIN Or acet 4-PHENYLENE diamin, etc., coupled in acetic soln. with 2-ANISIDIN, 
product diazotized and coupled in alk. carb. soln. with 2-amino 8-NAPHTHOL 6-sulfo, or other. 
Blue-BLackK to BLUE and red-or green-BLACK direct and developed dyes that can be diazotized on 
fiber and coupled with 2-NAPHTHOL, etc., and are then fast to acids, light, washing and level dyeing. 


1,365,706—Jan. 18, 1921. Herbert LEvINSTEIN and James BappiLEey, England. 
Production of fast shades on vegetable fibers and dyestuffs therefor. 


3.3’-Azoxy di-aANILIN tetrazotized and coupled in alk. soln. with 3’-amino benzoyl 2-amino 5- 
NAPHTHOL 7-sulfo, rediazotized and coupled with 2 mols. REsoRcIN. Other neuclei of two 
amino aryl radicals united by various groupings such as ethylene, azo, azoxy, sulfur, 
oxygen, thio carbonyl, ethylene dioxide or phenyl diethers are claimed. RED, ORANGE 
Or BROWN direct and developed dyes, fast to boiling soap when developed by formaldehyde. 

Note Ser. 804,117. 


1,371,979—Mar. 15, 1921. Re. 15,182—Aug. 23, 1921. 
Walter M. Raupu, New York. (National.) 


Disazo dye. 


1-Amino 4-nitro NAPHTHALENE 6- or 7-sulfo (or nitro Cleve’s acid), coupled in HCI soln. 
with 2-amino 4-crESOL, methyl ether, separated and again diazotized and coupled in alk. carb. 
soln. with 2-AMINO 8-NAPHTHOL 6-sulfo “Gamma,” and reduced at 70° with Na,S. Brive and 
blue-BLAcK to green-BLACK direct and developed dyes, that may be diazotized and coupled on 
fiber with various developing agents. 


186 DIGEST OF PATENTS 


1,372,439—Mar. 22, 1921. Thomas H. Ltaminc, New York. (National.) 
Azo dye. 

Acet 4-PHENYLENE DIAMIN coupled in acetic soln. with 1-AMINO 8-NAPHTHOL 4-sulfo ‘“S” 
saponified in 10 per cent NaOH, and in alk. carb. soln. coupled with diazo acet. 4-PHENYLENE 
DIAMIN. Green-BLACK direct and developed dyes that may be diazotized and developed on fiber 
with various coupling agents to give fast shades. 


1,375,701—Apr. 26, 1921. Carl JAGERSPACHER, Switzerland. (Basle.) 
Azo dyestuffs dyeing on mordants. 

2-Amino 4-chlor PHENOL 6-carbo acid, coupled in presence of Ca(OH), with 1.8-dioxy 
NAPHTHALENE 3-sulfo 6-carbo acid. ‘The 4-sulfo isomer of second component and other ortho- 
oxy diazo comps. are claimed. ViIoLET to BLUE or BLACK acid and developed (CrO,) or acid 
mordant (Cr) dyes, fast to soaping, Cl and light, and suitable for printing on Cr mordant. 


Note Ser. 297,095 (May 14, 1919). 


1,378,388—May 17, 1921. Theresa M. SusEm1HL, New York. (National.) 
Disazo dye. 

4-Amino ACETANILID, or 4-nitranilin, coupled in alk. carb. soln. with 2-amino 4-CRESOL 
methyl ether, again diazotized and coupled in alk. soln. with 2-AMINO 5-NAPHTHOL 7-sulfo ‘‘I”’ 
acid, and hydrolyzed at g0-100° in 10 per cent NaOH. BtveE to siack direct or developed 
dyes that may be coupled on fiber with 2-NAPHTHOL or other developer. 


1,382,196—June 21, 1921. Carl JAGERSPACHER, Switzerland. (Basle.) 
Azodyestufis dyeing on mordants. 


3-Amino 5-nitro SALICYLIC acid coupled in conc. soln. of 1-NAPHTHOL 3-sulfo 6-carbo acid 
in presence of Na,CO, and NaOH. Ortho oxy diazo comps. which combine in ortho position 
to the OH group without splitting off the COOH group of the above coupling agent are 
claimed. Rrp, BROWN to VIOLET acid, acid mordant (Cr) and developed (CrO,) dyes, fast to 
soap, Cl and light when printed on chromium mordants. 


1,383,710—July 5, 1921. Allan James FirLp, New York. 
Dyestuff and process of making the same. 


ToLIpIN coupled with 2 mols. of mixed 2-NAPHTHOL 6- and 8-sulfo acids, derived from 
2-NAPHTHOL heated at 100° with 100 per cent H,SO, (The 2.6-comp. predominates.) Dye 
is pptd. as the copper salt with CuSO, and purified pulp mixed with dextrin to render it soluble. 
Different proportions of two sulfo acids give more violet (2.8) to greener (2.6) shades. BLUE 
lake dye, faster when combined with a copper salt. 


1,3883,711—July 5, 1921. Allan J. Firztp, New York. 
Monoazo dyestuff. 


2-NAPHTHYLAMINE 1-Sulfo acid coupled in alk. soln. with 1-AMINO 8-NAPHTHOL 3.6-disulfo 
acid. A violet RED acid dye. 


1,394,823—Oct. 25, 1921. Armin Gros, Switzerland. (Basle.) 
Green acid dyestuffs containing chromium and process of making same. 


5-Nitro 2-amino PHENOL azO 2-NAPHTHYLAMIN 6-sulfo, or other ortho oxy azo comps. con- 
taining as second component a 2-naphthylamin not substituted in the 1-position, boiled in dil. 
CrF, soln. (36.8 per cent Cr,O,) or equivalent chromium comp. in presence of sod. silicate or 
acetate or ammonium lactate, etc. to bind the dcids that are liberated. GREEN acid or acid mor- 
dant dye, containing chromium within the molecule, fast to acids and to metals. 

Note 1,227,406. 


1,395,238—Oct. 25, 1921. Robert Arnot, Switzerland. 
Azo dye and its process of manufacttre. 

One part RETENE is nitrated in 3 parts fuming HNO,, reduced in conc. ale. NaOH by 
boiling with hydrosulfite to which HCl is slowly added until in excess, and dissolved retene 
amin coupled with the usual coupling agents. Retene quinone or retene sulfo acid may be 
treated in similar manner. RED to VIOLET to BROWN acid dyes. 


GROUP VI.—AZO 187 


1,402,350—Jan. 3, 1922. Joseph GRIMMER and Fritz Srraus, Switzerland. (Basle.) 
Chromium compounds of azo dyestufts. 

1-Amino 2-NAPHTHOL 4-sulfo or deriv. coupled in alk. soln. with 8-chior 1-NAPHTHOL or 
other halogen deriv. of 1-naphthol and separated dye refluxed in alk. soln. of Cr,0, containing 
glycerin to form a chromium comp. Red VIOLET to GRAY or BLUE fast acid dyes containing 
Cr. in molecule. With copper comps. dye is violet. 


1,405,687—Feb. 7, 1022. Rudolph Haucwitz, Germany. (Berlin.) 
Azo dye. 


ANILIN 3-sulfo or other amino aryl sulfo acid of benzene series, coupled in alk. carb. soln. 
with 8-oxy QUINOLIN 5-sulfo acid. YELLOW, ORANGE to BROWN developed (CrO,) dyes. 


1,408,296—Feb. 28, 1922. Wilhelm Hrerzperc and Oswald ScHARFENBERG, Germany. (Berlin.) 
Orthooxyazo dyes for wool. 
2-Amino 4-nitro 6-chlor PHENOL coupled in alk. carb. soln. with 8-chlor 1-NAPHTHOL 5-sulfo. 


Other 2-amino phenols containing negative radicals in nucleus and other 8-chlor-1-naphthols are 
claimed. Brack acid or acid mordant (Cr) dyes. 


1,408,297—Feb. 28, 1922. Wilhelm Herzprerc and Oswald ScHARFENBERG, Germany. (Berlin.) 
Orthooxyazo dyes. 


3.4.5-Trichlor 2-amino PHENOL or other polyhalogen deriv. of ortho amino phenol, coupled 
in alk. soln. with acetyl 1-AMINO 8-NAPHTHOL 4-sulfo or other peri amino naphthol. Brive acid 
mordant (Cr) dyes. 


1,408,363—Feb. 28, 1922. Werner Lance, Germany. (Berlin.) 
Ortho-oxymonoazo dyes. 


Picramic acid coupled in alk. soln. with 4-methyl acetyl 2-amino PHENOL or other ortho 
amino phenol substituted by a univalent radical in 4-position. Green BRowN acid mordant (Cr) 
dyes. 


1,408,405—Feb. 28, 1922. Bernard ScHONER and Otto S1EBERT, Germany. (Berlin.) 
Azo dyes. 


Acetyl 6.3-diamino PHENOL 4-sulfo. methyl ether, coupled in acetic soln. with 2-amino 8- 
NAPHTHOL 6-sulfo acid. The first component may be coupled as a nitro deriv. then reduced 
and alkylated or acetylated etc. Violet rEp acid dyes. 


1,411,245—Mar. 28, 1922. Hugo GELDERMAN and Felix Mryer, Germany. (Berlin.) 
Azo dye. 


1-Amino 7-NAPHTHOL heated with PHTHALIC anhyd. in benzene soln. and resulting 2’- 
carbo. benzoyl 1-AMINO 7-NAPHTHOL coupled in alk. soln. with diazo 4-nitro 2-amino PHENOL or 
other. ortho amino phenol deriv. Green-prown acid mordant or developed (CrO,) dyes, fast 
to milling. An ammonium salt should.sbe present in dye bath. 


1,414,614—Apr. 25, 1922. . Robert Arnot, England. 
Dye and process of making same. 


Impure axBiEtTIc acid, or colophony or other resin, is nitrated in fuming HNO, at 100°, 
reduced to amino comp. by hydrosulfite, or it is first sulfonated then nitrated and reduced. 
Products can be used by themselves as dyes or diazotized and coupled to form azo dyes or 
may be used as coupling agents. VARI-COLORED acid and acid mordant (Fe) or developed 
(coupled) dyes. 


- 


1,415,704—May 09, 1922. Walter M. Ratpu and Lawrence H. Fierr, New York. (National.) 
Production of disazo dye. 


_4-NITRANILIN equivalent to 2 mols. in hot HCl soln. is powdered into nitrite soln. at 0° 
and to the resulting HCl soln. of diazo comp. is added 1 mol. 1-amino 8-NAPHTHOL 4-sulfo, 
which couples with 1 mol. of the diazo body and when soln. is neut. with sod. acetate com- 
bines also with a second mol. to form a dinitro disazo deriv. that is reduced by Na,S to the 
diamino product. Green siacKx direct or developed dye that may be coupled on fiber with 2- 
naphthol, etc. 

13 


188 DIGEST OF PATENTS 


1,416,621—May 16, 1922. Jens DrepicHen, Germany. (Berlin.) 
Manufacture of diazotizable trisazo dyes. 


METANILIC acid or other amino aryl sulfo acid is coupled with 1-NAPHTHYLAMIN HCl, 
coupled again in acetic soln. with 1-NAPHTHYLAMIN 6- or 7-sulfo and coupled a third time in 
alk. soln. with 2-aMINO 8-NAPHTHOL 6-sulfo. Middle components may be sulfonated or other- 
wise substituted. End component remains the same. BLUE to GREEN basic or developed dyes 
that may be coupled on fiber. 


1,419,500—June 13, 1922. Rudolph Hauewitz, Germany. (Berlin.) 
Orthooxyazo dyes. 


2-Amino PHENOL 4-sulfo or deriv., is coupled in alk. soln. with 8-oxy QUINOLIN or deriv. 
Brown to RED or vioLET acid or developed (CrO,) dyes, fast to washing and milling when 
chromed. 


1,419,501—June 13, 1922. 
Wilhelm HeErzserG and Oswald ScHARFENBERG, Germany. (Berlin.) 
Orthooxyazo dyes. 


2-Amino 4.6-dichlor PHENOL or other ortho amino phenol with negative substituents, coupled 
in alk. soln. with 8-chlor 1-NAPHTHOL 5-sulfo. Buur acid mordant (Cr) dyes. 


1,422,866—July 18, 1922. Heinrich JorpaAn, Germany. (Grasselli.) 
Cotton dyes. 


Acetyl 4-amino I-NAPHTHYLAMIN 6- or 7-sulfo coupled in acid soln. with 1-NAPHTHYLAMIN 
6- or 7-sulfo, again coupled with 2-NAPHTHOL, or 2.7-dioxy naphthalene, product hydrolized in 
dil. NaOH and finally coupled with REsorcin. Green BLUE direct or developed dyes, fast to 
light, and rendered fast to washing by after treatment with formaldehyde. 


1,426,189—Aug. 15, 1922. 
Wilhelm Herzperc and Oswald ScHARFENBERG, Germany. (Berlin.) 
Ortho-oxyazo dyes. 


3.4.6—Trichlor 2-amino PHENOL or other polyhalogen ortho amino phenol, coupled in alk, 
soln with 1-naphthol 4-, 5- or 6-sulfo. Violet-sLuE to vioLEetT acid mordant (Cr) or developed 
(CrO, and NH, salt) dyes, fast to light, washing and milling. 


1,426,190—Aug. 15, 1922. 
Wilhelm HeErzserc and Osward SCHARFENBERG, Germany. (Berlin.) 


Ortho-oxyazo dyes for wool. 


3.4.6-Trichlor 2-amino PHENOL, the 3.4.5 or other polyhalogen deriv., coupled in alk. soln. 
with I-AMINO 8-NAPHTHOL-2.4 disulfo or other unsubstituted amino deriv. of naphthol sulfo 
acids. Green BLUE acid mordant (Cr) dyes, fast to light, washing and milling. 


1,429,781—Sept. 19, 1922. Hugo ScHWEITZER, Germany. (Bayer.) 
Blue wool dyestuff. 


4-NITRANILIN 2-sulfon ethyl amilid is diazotized in glac. acetic soln. and coupled with 2- 
AMINO 8-NAPHTHOL 6-sulfo with excess HCl present. Derivs. are claimed. Buus acid dyes, 
fast to light and fulling. 


1,429,782—Sept. 19, 1922. Hugo ScHWEITZzER, Germany. (Bayer.) 
Reddish-violet monoazo dye for wool. 


4-NITRANILIN 2-sulfon ethyl amilid or derivs. diazotized in glac. acetic acid, coupled in 
presence of excess sod. acetate with 2-NAPHTHYLAMIN 8-sulfo. RED to vioLEtT acid dyes, fast to 
light and fulling. 

Note 1,429, 781. 


1,431,655—Oct. 10, 1922. Wilhelm Herzsperc and Oswald ScHARFENBERG, Germany. (Berlin.) 
Orthooxyazo dye. 


3.4.5-Trichlor 2-amino PHENOL, or other ortho amino phenol containing negative substit- 
uents such as Cl, coupled in alk. soln. with 8-chlor 1-NaAPHTHOL 5-sulfo or other. Fast BLUE 
acid mordant (Cr) dyes. 


GROUP VI.—AZO 189 


1,437,758—Dec. 5, 1922. Carl JAcERSPACHER, Switzerland. (Basle.) 
Dyestuffs particularly adapted for calico printing. 


I-AMINO 2-NAPHTHOL 4-sulfo is coupled with REsoRcyLic acid in alk. carb. soln., 30 per cent 
NaOH added, then pptd. by excess HCl. Dark powd. sol. in aq. (RBr), with alk. carb. (V) in 
conc. H,SO,(V); a violet BLUE acid mordant (Cr) dye, fast to soap and light, suitable for print- 
ing. The nitro and other derivs. of the amin are also claimed. 


1,447,485—Mar. 6, 1923. Emil Reser, Switzerland. (Basle.) 
Coloring matters derived from pyrazolone. Anilin azo 2/-methyl 3/-sulfo 5’-isopropyl 


phenyl methyl pyrazolone. 

ANILIN is coupled in alk. carbonate soln. with the product of condensation of aceto acetic 
ester and the hydrazin of 2-amino cymor 6-sulfo. Yellow powd., yELLow acid dye, fast to light. 

Near S. 23—‘‘Tartrazin.”’ 


1,452,083—Apr. 17, 1923. August L. Lasxka and Arthur ZitscuEer, Germany. (Griesheim.) 
Black azo dyestuffs and process of making same. (Process not claimed.) 


4-Ethoxy 3-TOLUIDIN azo I-NAPHTHYLAMIN is coupled in alk. soln. with one mol. 3-oxy 
2-NAPTHOIC 4’-anisidid. Other aryl azo 1-naphthylamin comps. not containing sulfo groups and 
aryl amids of 3-oxy 2-naphthoic acid are claimed. Methods of application to fiber as devel- 
oped dye are given. Black metallic powds., insol. in aq., sol. conc. H,SO, (B-G); Biack de- 
veloped dyes. 


1,453,660—May 1, 1923. 
Guillaume de Montmotiin, Gerald Bonuore and Josef SpienEer, Switzerland. (Basle.) 
Azo dyestuffs and process for the manufacture of same. 


2-Amino PHENOL 4-sulfo, methyl ether, is coupled in alk. soln. at 0° with 2 parts (equimol) 
4.4'-dioxy DINAPHTHYL ketone 3.3’-dicarbo. CO, is eliminated. Other amino derivs. preferably 
unsulfonated and other unsulfonated 4-oxy naphthalene 1-aryl ketones are claimed. ORANGE to 
violet RED developed dyes. 


1,457,114—May 29, 1923. August L. Lasxa and Arthur ZitscHer, Germany. (Griesheim.) 
Azo dyestuffs and process of making same. 


2.5-Dichlor ANILIN or other amino deriv. is coupled in alk. soln. with 3-oxy 2-NAPHTHOIC 
2/-anisidid or derivs. Orange to blue to black powds., insol. aq., sol. in H,SO, (V-G); oraNcE 
to RED developed dyes, suitable for lakes and printing. 


1,457,235—May 29, 1923. Richard Stiisser, Germany. (Bayer.) 
Azo dyestuffs. 


4.4’-Diamino DIPHENYL 3.3’-dicarbo is tetrazotized and coupled with 1 mol. each of two 
different components of which one contains sulfo or carbo groups, such as phenyl 2-NAPTHYL- 
AMIN and 5,.5/-dioxy 2.2’-DINAPHTHYLAMIN 7.7/-disulfo. Dark powds. sol. aq. (V), in conc. 
sulf. (B); vari-coLorED direct dyes that are bluer and faster to light and washing when after 
treated with CuSQ,. 


1,467,711—Sept. 11, 1923. Guillaume de MonrMo.uin, Switzerland. (Basle.) 


Process for the manufacture of intermediate products and new dyestuffs 
derived from diarylsulphones. (Product, not process, claimed.) 


2-Amino 4-acetyl amino 4/-methyl 5’-sulfo pIPHENYL sulfone or other ortho amino diaryl 
sulfone is coupled in acid soln. with ethyl 2-NAPHTHYLAMIN or any non sulfonated aromatic 
amin of at least 10 carbon atoms in the nucleus, or derivs. Orange to brown powds., sol. in 
aq. (O-VR), in H,SO, (Y-Br-V); orancE to violet RED acid dyes, fast to light and washing. 


1,472,833—Oct. 30, 1923. A. Willard Joycr, New Jersey. (Chem. Found.) 
Disazo coloring matter. 


4.4'-Diamino DIPHENYL ketone, prepared in usual manner by refluxing diamino DIPHENYL 
methane with Na,S and S, is dissolved in 500 parts aq. and 50 parts conc. HCl soln. cooled to 
5-10°, tetrazotized and coupled in dil. sod. carbonate with 55 parts NAPHTHIONIC acid, Na salt. 
Other ketones and naphthalene derivs. are claimed. Orange rED to vioLwET direct dyes, level 
and fast to light, acids, alks., washing and milling. 


190 DIGEST OF PATENTS 


1,472,334—Oct. 30, 1923. A. Willard Joycr, New Jersey. (Chem. Found.) 
Disazo dyes. 
Patent is similar to 1,472,333 and claims a tetrazo deriv. of a 4.4’-diamino pDIARYL ketone 


coupled in alk. soln. with a NAPHTHOL which may contain sulfo, oxy or halogen groups. Orange 
RED tO VIOLET direct dyes, fast to light, washing and milling. 


1,474,587—Nov. 20, 1923. Carl H&EIDENREICH, Germany. (Bayer.) 
Azo dyestuffs. 

4-PHENYLENE DIAMIN 2.6-disulfo, Na salt, in 4 parts aq., with 0.5 parts HCl is diazotized and 
coupled in alk. soln. with a phenol ortho carbo acid such as SALICYLIC or CRESOTINIC acid. YEL- 
Low acid mordant (Cr) dye. 


Group VII—INDIGO AND INDIGOID. 


Patents claiming materials which with one or two operations that do not 
introduce further organic constituents will yield an indigo are included among 
indigo dye patents, not with intermediates. 


227,470—May 11, 1880. Adolf Baryrer, Germany. 

Manufacture of artificial indigo. (Product also claimed.) Indigo from acrylic or 
propiolic acid. 

2-Nitro phenyl oxy acrylic acid or 2-nitro phenyl ProPioxic acid heated carefully to 100-1209 


with alk. and glucose or other deoxidizing agent. 
S. 874—“‘Indigo.”? Note 228,300 and 240,359. 


228,300—June 1, 1880. Adolf Baryrer, Germany. 


Manufacture of artificial indigo-blue. (Product also claimed.) Indigo blue on fiber, 
and process therefor. 
2-Nitro phenyl propionic acid or 2-nitro phenyl oxy acryLic acid, together with glucose and 
alkali, or other reducing agent padded on fiber, then developed by steaming, etc. 
S. 874—“‘Indigo.’? Addition to 227,470. 


233,458—Oct. 19, 1880. Adolf Batyrer, Germany. 


Manufacture of artificial indigo. (Product also claimed.) Dibrom 2-nitro cinnamic 

or propiolic acids. 

2-Nitro CINNAMIC acid converted to 2-nitro dibrom hydro cCINNAMIC acid by treatment with 
Br, with or without a solvent. Alkalies in alc. soln. form 2-nitro phenyl ProPioLic acid which 
when heated in alk. with deoxidizing agents (glucose, milk sugar, etc.) yields indigo. Product 
is a whitish, cryst. solid, easily sol. in organic solvents except petroleum hydrocarbons, a 
strong acid, decomp. by heat into HBr and indigo or heated with alk. and reducing agent first 
yields 2-nitro phenyl proprio.tic acid, then indigo. 

S. 874—‘“Indigo.” Note 238,459 and 60. 


233,459—Oct. 19, 1880. Adolf Bartyrer, Germany. 


Process for producing artificial indigo. (Product also claimed.) 2-nitro phenyl oxy 

acrylic acid. 2 

2-Nitro CINNAMIC acid or other in alk. carbonate soln., Cl or Br. added, excess halogen re- 
moved by sulfurous acid, soln. made strongly acid with HCl, filt. and extracted by ether to 
obtain 2-nitro phenyl chlor Lactic acid, which, with alc. KOH, forms 2-nitro phenyl oxy AcRYLIC 
acid. Product is a white cryst. solid, sparingly sol. in aq., a strong acid, heated to fusion forms 
indigo. 

S. 874—“Indigo.’”? Note 233,458. 


233,460—Oct. 19, 1880. Adolf Bartyrer, Germany. 
Process for the production of artificial indigo. (Product also claimed.) 2-nitro 
phenyl propiolic acid. 
2-Nitro CINNAMIC acid or derivs., dihalogenated at usual temp., then heated with alc. KOH 
to form 2-nitro phenyl Propionic acid, which, heated with glucose and alk., forms indigo. Product 


GROUP VII.—INDIGO AND INDIGOID IQI 


is a white cryst. solid, easily sol. in alc., sparingly sol. in cold aq., a strong acid, when mixed 
on fiber with alk. and deoxidizing substances, indigo is developed by dry heat or steam. 
S. 874—“Indigo.” Note 233,458. 


235,193—Dec. 7, 1880. Adolf Baryrer, Germany. (Badische.) 


Manufacture of artificial indigo. (Product also claimed.) Indigo deriv. from 2-nitro 

phenyl propiolic acid and sulfuric acid. 

2-Nitro phenyl Propionic acid acted upon by conc. sulfuric (sp. cr., 1.84) below 20° until a 
test with glucose and alk. gives no indigo, then reduced with FeSO,, or other. A BLuE vat dye 
that resembles vegetable indigo and is dyed in similar way; is sol. in aniline at usual temp. and 
in aq. H,SO,. 

S. 877—“Indigo G.” Note 235,488 and 233,460. 


240,359—Apr. 19, 1881. . Adolf Bartyer and Heinrich Caro, Germany. (Badische.) 
Manufacture of artificial indigo. (Product also claimed.) Indigo from 2-nitro 

phenyl propiolic acid. 

2-Nitro phenyl propionic acid converted to alk. comp., mixed thoroly in aq. paste with sod. 
xanthate and allowed to dry spontaneously till blue color develops, then purified by washing. <A 
BLUE vat dye with same properties as indigo of 227,470, but containing free sulfur. 

S. 874—“Indigo.” Note 227,470, 233,458, 240,360 and 240,361 (Appl). 


240,941—May 3, 1881. Adolf Bartyer, Germany. (Badische.) 
Manufacture of artificial indigo. (Product also claimed.) Indigo from isatin. 
IsaTIN converted to chloride by PCI, in benzene soln. at 80° and product in glac. acetic soln. 


reduced by Zn. dust, or other, then oxidized by air. 
S. 874—‘Indigo.” 


240,942—May 3, 1881. Adolf BaryEr and Adolf EmMmeErtinc, Germany. (Badische.) 
Manufacture of artificial indigo. (Product also claimed.) Indigo from isatin. 
IsaTIN, finely divided, heated in ‘pressure vessel at 70-80° with mixture of PCl,, CH,COCI 


and yellow phosphorous, diluted and oxidized in air. 
S. 874—‘Indigo.” 


250,035—Nov. 22, 1881. Adolf Baryer, Germany. (Badische.) 
Manufacture of artificial indigo. (Product also claimed.) Indogenic acid. 

2-Nitro phenyl propionic acid, ethyl ester, reduced with cold soln. NH,SH, pptd. by acid, 
product exhausted with cold dil. NaOH and INnpDoGEN ester pptd. by acid. ‘This ester is heated 
in NaOH to 160-180° until all alc. is driven off and indogenic acid is then pptd. by acid. With dil. 
alk., ammonia or acid oxidizer indogenic acid readily forms indigo. 

S. 874—“‘Indigo.”’ Note 250,036. 


250,036—Nov. 22, 1881. Adolf Bartyer, Germany. (Badische.) 
Manufacture of artificial indigo. (Product also claimed.) Indogen. 

2-Nitro phenyl propiotic acid ester, treated as in 250,035 to form INDOGENIC acid, which on 
heating to 122° decomp. into indogen and CO,. Product is an oily liq., sol. hot aq., nonvolatile 


with steam, readily converted in alk. soln., with air or acid oxidizers, into indigo. 
S. 874—“‘Indigo.” 


251,499—Dec. 27, 1881. Adolf Baryrer, Germany. (Badische.) 
Manufacture of artificial indigo. (Product, not process, claimed.) Indigo from 2- 

nitro-acetenyl benzene. 

2-Nitro phenyl propioiic acid, dist. with steam to separate CO, and form 2-nitro acetenyl 
BENZENE (collected in distillate), which, when boiled with bisulfite, forms a sulfo acid that may 
be heated with reducing agents to form indigo. Ammoniacal cuprous chloride forms a red 
copper lake. 

S. 874—‘‘Indigo.”’ 


251,500—Dec. 27, 1881. Adolf Baryer, Germany. (Badische.) 
Manufacture of artificial indigo. Diisatogen. 


Ortho dinitro acetenyl BENZENE treated with conc. then fuming sulfuric acid to form ptsa- 
TOGEN, which is pptd. by aq. or alc. Diisatogen is a red cryst. solid, almost insol. in alc. etc., 


192 DIGEST OF PATENTS 


sparingly sol. in CHCl,, and easily sol. in anilin, phenol and hot nitro-benzene, quickly con- 
verted to indigo on reducton. 


S. 874—‘“Indigo.” Note 251,671 for formation of ortho-dinitro acetenyl benzene. 


251,501—Dec. 27, 1881. Adolf Baryer, Germany. 


Manufacture of soluble derivatives of indizgo-blue. (Product also claimed.) 
Indigo white sulfo deriv. 


Inp1co heated in closed vessel with caustic alk., ferrous sulfate and pyrosulfate of potash to 
form the sulfo acid, a sol. deriv., which is readily sol. in aq. and easily decomp. by mineral 
acids or converted into indigo by acid oxidizing agents. 

S. 877—“Indigotine Ia’’ (leuco). 


251,.671—Dec. 17, 1881. Adolf Bartyer, Germany. 


Preparation of new material for the manufacture of artificial indigo. 
(Product, not process, claimed.) Dinitro diacetenyl benzene. 


2-Nitro phenyl PRopioiic acid distilled with steam to form 2-nitro acetenyl BENZENE and CO,. 
Copper salt is formed and treated with KOH and ferricyanide in aq. soln., filt. and chloroform 
soln. distilled to give dinitro diacetenyl BENZENE in distillate. It is yellow cryst. solid, fusible 
at 212°, insol. in aq., ether, cold alc., sparingly sol. in hot alc., CS,, acetone, and benzene, easily 
sol. in hot nitro-benzene, diff. sol. in conc. H,SO,, but dissolves readily upon addition of fuming 
H,SO,, with a red color, as Diisatogen. 

S. 874—“Indigo.” Note 251,500. 


257,812—May o, 1882. Adolf BArYER and Viggo B. Drewson, Germany. (Badische.) 
Preparation of material for manufacture of artificial indigo. 2-Nitro cin- 

namyl formic acid. 

2-Nitro BENZALDEHYDE heated with PYRORACEMIC acid (pyruvic) cooled below 10°, sat. with 
dry HCl, then let stand 2 or 3 days till solid. 2-Nitro cinnamyl formic acid is a whitish cryst. 
solid, easily sol. in alc., sparingly sol. cold aq., a strong acid which in alk. soln. readily forms 
indigo. 

S. 874—‘Indigo.” Note 257,813 and 14 for product patents. 


257,813—May o, 1882. Adolf BaryEr and Viggo B. Drewson, Germany. (Badische.) 
Preparation of material used in the manufacture of artificial indigo. 

(Product, not process, claimed.) 2-Nitro cinnamyl formic acid. 

2-Nitro BENZALDEHYDE, condensed with pyrocEMic acid by heat, then dry HCl gas passed 
through the mixture. 

S. 874—“‘Indigo.” Note that this is a product patent for 257,812. 


257,814—May o, 1882. Adolf BatyEer and Viggo B. Drewson, Germany. (Badische.) 
Manufacture of artificial indigo. Indigo from 2-nitro benzaldehyde. 

2-Nitro BENZALDEHYDE, I part, and ACETONE, 15 parts, condensed in dil. NaOH at usual temp. 
Other alk. agents may be used, and acetic aldehyde, pyroacemic acid, or analogous bodies instead 
of acetone claimed in other patents. 

S. 874—“Indigo.” Note 257,813 and 227,470. 


257,815—May o, 1882. Adolf Baryer and Viggo B. Drewson, Germany. (Badische.) 
Artificial indigo. Indigo from 2-nitro benzaldehyde. 

2-Nitro BENZALDEHYDE condensed with AcETONE in dil. alk. soln. Has greater purity of color 
than veg. or other artificial indigo and no red or purple component sol. in alc. 

S. 875—“‘Indigo Salt T.”? Note 227,470, 257,812-14 and 540,427 (Kalle). 


259,260—June 6, 1882. Adolf Batyrr, Germany. (Badische.) 
Process of manufacture of indigo-blue. Indigo from indogenic acid. 


2-Nitro phenyl Propro1ic acid, ethyl ester, treated with NH,SH cold, filt. extracted with cold 
soln. alk., pptd. with acid, fused with hot conc. NaOH at 160-180°, then pptd. by acid as IN- 
DOGENIC acid which may be oxidized in alk. soln. by air or in acid solns. by FeCl,, CrO,, etc., 
to form indigo. 

S. 874—‘“Indigo.” 


GROUP VII.—INDIGO AND INDIGOID 193 


259,261—June 6, 1882. Adolf Baryrer, Germany. (Badische.) 
Process of manufacture of indigo-blue. Indigo from indogenic acid. 


2-Nitro phenyl propionic acid ester, treated as in 259,260 to produce INDOGENIC acid, which 
is fused to remove CO, and form 1npocEN, then oxidized in alk. soln. with air or in acid soln. 
with FeCl,, etc. 

S. 874—‘Indigo.” Note 259,260. 


259,629—June 13, 1882. Adolf BaryEr, Germany. (Badische.) 
Manufacture of artificial indigo. (Product claimed.) Indigo from toluene. 


ToLUENE boiled, Cl gas passed in (37.5 per cent), product dist. and portion 170-180° (BENZYL, 
chloride) boiled with KCN in alc., to form BENzyL cyanide, heated in closed vessel to 140° with 
acid to form PHENYL acetic acid, nitrated, reduced to 2-amino PHENYL acetic (or OXINDOL), 
nitroso oxindol formed, reduced to amino oxindol, oxidized to IsaTIN which with PCI, in, dry 
benzol soln. will form isatin chloride, then heated in glac. acetic soln. with Zn. dust to decoln., 
oxidized by air and pptd. by aq. to form indigo. 

S. 874—“Indigo.” 


262,695—Aug. 15, 1882. Christian RupoLpH, Germany. (Héchst.) 
Manufacture of artificial indigo. (Product claimed.) Indigo from  benzylidene 
acetone. 


BENZYLIDENE acetone (by condensing BENZALDEHYDE and ACETONE in dil. NaOH.) nitrated, 
the ortho and para nitro derivs. separated by crystn. of latter from alc. soln. and the 2-nitro 
BENZYLIDENE acetone digested in alc. NaOH, until new product is formed. Indigo results when 
new product is boiled in aq. or dil. alk. 

S. 874—“Indigo.” Note 276,889 and go. 


276,8S88—May 1, 1883. Christian RupoLpH, Germany. (Hochst.) 
Manufacture of cinnamie acid. Cinnamic acid and derivs. 


BENZYLIDENE acetone heated gently with bromine in 4 per cent NaOH soln., bromoform being 
separated, then soln. made acid and pptd. cinnamic. acid cryst. from alc. Reference is made to 
chlorine deriv., using hypochlorites, claimed by another patentee. 

S. 874—‘Indigo.” 


276,889—May a, 1883. Christian RupotpH, Germany. (Héchst.) 
Material for the manufacture of metamethyl indigo. (Process claimed.) 2-Nitro 

5-tolyl aldehyde for 5.5’-dimethyl indigo. 

3-ToLy. aldehyde, from 3-XYLENE, nitrated at 15° to form ortho nitro deriv. Product is a 
yellowish oil, sparingly sol. in aq., easily sol. in alc., benzene, ether, acetone, combines with bi- 
sulfite, and may be used directly to produce methyl indigo. 

Note 262,895, and for mfr. of derived indigo, see 276,890. 


276,890—May 1, 1883. Christian Rupotpu, Germany. (Hdéchst.) 


Manufacture of metamethyl indigo. (Product, not process, claimed.) 5.5’-Dimethy] 

indigo. : 

3-To.yL aldehyde nitrated and resulting 2-nitro 5-tToLyL aldehyde dissolved in acETronE or 
ethyl aldehyde, to which 2 per cent NaOH is added. Dye is formed promptly. Methyl indigo 
resembles natural indigo in its physical properties. It has a dark blue color, with coppery luster, 
differs from natural product in being sol. in alc., and is destroyed by HNO,. 

S. 888—‘Indigo M. L. B.”? Note 262,695 and 276,889 for mfr. of aldehyde. Schultz credits 
this dye to Koetschet, 1893, 662,073. 


310,604—Jan. 13, 1885. Paul J. Meyer, Germany. 
Manufacture of isatins and substituted isatins. Isatin and derivs., such as 4- 
tolyl 5-methyl isatin, methyl group being in benzene nucleus of isatin, not as methyl ether. 


4-TOLUIDIN, 4 mols., heated with 2 mol. dichlor acETic acid, with or without solvent, the 
separated product oxidized with air to 4-toluidin 5-methyl 1sat1n, which, with strong acids or 
alk. at common temp. yields 4-toluidin and 5-methyl isatin. Other halogen acetic acids, and esters, 
amines, aldehydes, etc., claimed. Para methyl isatin has properties like isatin, is sol. in alc., 
acetic acid, aq., and H,SO,, converted to HCl salt and reduced, the para methyl indigo that 
results is similar in properties to natural indigo. 


194 DIGEST OF PATENTS 


§24,256—Aug. 7, 1894. Rudolph Kwigrscu, Germany. (Badische.) 
Blue dye. (Process claimed.) Indigo sulfo acids. 


Phenyl Giycocot mixed at 20°-30° with fuming H,SO, (70-100 per cent free SO,) then 
diluted (a) by adding weaker acid thereto, or (b) adding to more dil. acid, (a) being more highly 
sulfonated than (b) (disulfo). A siuk acid dye for wool, sol. aq. and alc., insol. ether and 
benzene. 

Near S. 877—“‘Indigo Carmine,” and S. 878—‘“Indigotine P.” 


540,427—June 4, 1805. Eugen Fiscuer and Julius Oppermann, Germany. (Kalle.) 
Indigo-salt and process of dyeing with same. Bisulfite compound of 2-nitro phenyl 

lacto-ketone, or ‘‘Indigo salt.”’ 

2-Nitro phenyl LacTto KETONE, produced by action of NaOH on AcETONE and 2-nitro BENZALDE- 
HYDE, dissolved in 40 per cent bisulfite at 40-50°, filt. and cooled to thick cryst. paste. Fibers 
impregnated with soln. of paste form indigo dyeings by further action of alkali. 

S. 875—‘“‘Indigo Salt, T.” Note 257,815. 


540,564—June 4, 1805. Leonhard Wacker, Germany. (Badische.) 
Bloe acid dye. (Process claimed.) Sulfonated indigo. 


3-Amino PHTHALIC acid is condensed with chlor acetic acid by heating in alk. soln. on water 
bath till solid, the resulting phenyl GLycocor 2-3-dicarbo acid (a yellow acid dye) fused in KOH at 
250-260°, and oxidized in alk. soln. Resulting carboxylated indigo is a blue green powd., insol. in 
aq., alc., ether, benzene and conc. HCl; sol. in conc. H,SO,; sol. in alk. (B), alk. salt forms 
coppery blue needles, decomp. by strong alk. or reducing agents; careful reduction gives leuco 
dye; a BLUE vat dye. When mono sulfonated in fuming 12 per cent H,SO, at 65° the second dye 
claimed by patent is produced,—sol. in aq. (GB), with NaC,H,O, (B), in strong alk. (Y), in conc. 
sulf. (G); a green BLUE acid dye. 

Near S. 877—‘“‘Indigo Carmine.”’ 


546,165—Sept. 10, 1895. Rudolph Knisetscu and Paul Semet, Germany. (Badische.) 
Indoxylic acid and process of making it. Indoxylic acid free from halogens and 
indoxyl. 


PHENYL GLycocoL 2-carbo acid, Na salt, dried, ground with 2 parts dry NaOH, heated 
in thin layers to 240-265°, excluding air by using atmosphere of inert gas, such as N, then 
ground, ice and dil. sulfuric added, indoxylic acid separated and dried below 50°, preferably ex- 
cluding air. Indoxylic acid is a grey powd., slightly sol. cold aq., sol. alc., ether and alk. aq., 
from which soln. indigotin is pptd. by oxygen. 

S. 874—‘Indigo.”” Note 534,560 (Heumann). 


617,651—Jan. 10, 1899. Livingston Girrorp, for Karl Heumann, Germany. (Badische.) 
Blue dye and process of making same. Homolog of indigo. 


Chlor acetic acid 1 mol. and ethyl anrLin, 2 mols., condensed at 110-115° to ethyl phenyl 
GLycoco, then fused in alk. at 350°, diluted and oxidized by air. A deep blue powd. with bronze 
streak, insol. aq., sol. in hot alc., benzene, ether, anilin, and glac. acetic (B-BG); a green BLUE vat 
dye that may be sulfonated to sol. acid dye. 

Near S. 874—‘“Indigo.”” Note 617,652 for modified process. 


617,65 2—Jan. 10, 1899. IL. Girrorp, for K. Heumann, Germany. (Badische.) 
Process of making indigo coloring-matter. Improved process for better yield of 
indigo. 


_ 2-Tolyl GLycocoL converted into indigo by using quicklime with caustic alk. in the fusion melt, 
in such quantity that melt is not too stiff to be stirred. Temp. should be 270-300° and air ex- 
cluded. 

S. 874—“Indigo.” Note 617,651, 619,883, 619,884, and 620,442, for homologs. 


618,096—Jan. 24, 18099. Bernhard Heymann, Germany. (Elberfeld.) 
Diacetyl indoxyl and process of making same. Diacetyl indoxyl m.p. 82°. 


Phenyl Giycin 2-carbo acid, disodium salt, added to boiling acetic anhyd., which when CO, 
ceases to evolve, is distilled off, residue washed, and heated with caustic alkalies to form indoxyl. 
Free phenyl glycin or its acetyl deriv. and alk. acetates may be used. Diacetyl indoxyl is a 
white powd. or colorless needles, m.p. 82°, nearly insol. aq., easily sol. alc., ether and acetone, 
yields indoxyl and indigo upon alk. oxidation. 

S. 874—‘“Indigo.” 


GROUP VII.—INDIGO AND INDIGOID 195 


619,883—Feb. 21, 1899. Livingston Grirrorp, for Karl Heumann, Germany. (Badische.) 
Dimethyl indigo and process of making it. Dimethyl indigo, and sulfo derivs. 


2-Tolyl GuycocoL, 1 part, heated with 2 parts caustic at 100°. Dimethyl indigo, like indigo, 
is a dark blue powd. with coppery luster; sublimes, insol. aq., slightly sol. not alc. and benzene; a 
green BLUE vat dye, greener than indigo. Sulfonated dye (see separate patent) gives redder 
shades than indigo sulfo. 

S. 874—“‘Indigo.” 


619,884—Feb. 21, 1800. Livingston Girrorp, for Karl HEumManN, Germany. (Badische.) 
Blue dye and process of making same. Homolog of indigo, and sulfo derivs. 


Ethyl 4-ToLUIDIN, 2 mols., heated at 1oo—120° with chlor acetic acid, x mol., to form ethyl 
4-tolyl Giycocot, which is separated as a yellowish oil and melted with caustic alkali at 300—-350° 
for 2-10 min., product being greener and more soluble in alc. the shorter the time of heating 
and higher the temp. A blue micro cryst. powd., largely sol. in alc., decomp. by excess alkali 
yielding 4-toluidin; a green BLUE vat dye resembling indigo. Sulfonated derivs. claimed. 

Near S. 874—‘“Indigo.”’ Note 617,651. 


620,442—Feb. 28, 1899. Livingston Girrorp, for Karl Heumann, Germany. (Badische.) 
Blue glycocol dye. (Process also claimed.) N-Diethyl 7.7’-dimethyl indigo and sulfo 
derivs. ; 


Chlor acrtic acid heated at 1o0-120° with ethyl 2-ToturpIn to form ethyl 2-tolyl GLycocoL, 
which is fused with alkali at 350°. Ethyl 2-tolyl glycocol recryst. from benzene has a m.p. of 63- 
64°, is easily sol. in alc., ether, benzene, glac. acetic and alk., not easily sol. in aq. Finished dye is 
nearly insol. in ale., decomp. on fusion in caustic, and is a green BLUE vat dye that may be sul- 
fonated to form a soluble BLUE acid dye. 

Near S. 888—‘‘Indigo MLB/T.” Note 617,651. 


620,562—Mar. 7, 18099. Rubin Buanx, Germany. (Cassella.) 
Amido malonie ester and process of making same. Substituted amino malonic 
acid esters. 


Brom or chlor Matontc acid, ethyl ester, 1 mol., mixed with 2 mol. ANILIN, or other aromatic 
amin. At high temps. products are transformed into indoxylic acid. esters. The malonic esters 
of anilin, m.p. 45°, 4-toluidin, m.p. 55°, and of 2-naphthylamin, m.p. 88°, are colorless crysts., 
insol. in aq., easily sol. in ordinary organic solvents. 

S. 874—‘Indigo.”? Note 620,563. 


620,563—Mar. 7, 1899. Rubin Bianx, Germany. (Cassella,) 
Process of obtaining indoxylic compounds of amido malonic esters. Indoxyl 
acid esters and sulfo derivs. 


Anilin MALONIc acid diethyl ester, or other, heated in paraffin bath at 200-270° until one mol. 
alc. is removed and mass thickens and becomes dark. 4-Toluidin and 2-naphthylamin derivs. 
of malonic acid are also claimed. 4-Tolyl indoxylic acid ester forms colorless crysts., m.p. 155—-6°, 
sol. in alc., benzene, and alkalies, and heated in conc. H,SO, forms the sulfo acids of 4-tolyl 
indigo. 2-Naphthyl indoxylic acid ester is a green yellow powd., m.p. 58°, with properties similar 
to the anilin and toluidin derivs. 

S. 874—‘Indigo.” Note 606,617 and 620,563. 


621,652—Mar. 21, 1899. L. Girrorp, for K. Hkumann, Germany. (Badische.) 
Blue dye. 7.7'-Dimethyl indigo sulfo. 


2-To.tuipiIn and chlor acetic acid condensed to 2-tolyl cirycocon, then fused in KOH at 300- 
340°, excluding air, diluted, oxidized, and the separated dimethyl indigo sulfonated. 7.7’-Dimethyl 
indigo sulfonic acid is a powd. like indigo carmine; is sol. in aq., slightly sol. in alc., insol. in 
ether, but is less sol. in glac. acetic than indigo carmine. 

Near S. 874—‘‘Indigo.” Note 617,651. 


622,139—Mar. 28, 1899. L. Girrorp, for K. Hrumann, Germany. (Badische.) 
Blue coloring-matter and process of manufacturing same. Indigo from phenyl 
glycocol or its derivs., and sulfo compounds thereof. 


Phenyl crycocot from chlor acetic and ANILIN, or other, heated above 260° with alkali, 
diluted and oxidized, then sulfonated or not. Product from phenyl glycocol is insol. aq., slightly 
sol. hot alc., ether, benzene, anilin and glac. acetic acid. 

S$. 874—‘“Indigo’” and homologs. Note 617,651. 


196 DIGEST OF PATENTS 


625,268—May 16, 1809. R. KwierscH and P. SrmeE,, Germany. 
Process of making indigo-red. Indirubin. 

Fheny! ciycocot 2-carbo acid or homolog, fused with alkali at 260-370° with sufficient amount 
of air to produce ISATIN or ISATINIC acid, then condensed with 1nroxyL. Mother liquors after re- 
moval of indigo in the usual indigo process, when boiled with fresh indigo melt, with liquor acid or 
alkaline, produce indigo red. 


626,231—June 6, 1890. Bernhard Heymann, Germany. (Elberfeld.) 
Proeess of making indigo. Indigo from diacetyl indoxyl. 
Diacetyl 1npoxyL saponified by heating at 100° in 5 per cent NaOH, then a current of air 


introduced till oxidized. 
S. 874—‘Indigo.” Note 618,096 for mfr. of diacetyl indoxyl. 


643,502—Feb. 16, 1900. H. S. A. Hort, Germany. (Badische.) 
Process of manufacturing indigo-leuco compounds. Indigo and derivs. 
ANTHRANILIC acid, salt or ester, heated with caustic alkali at 250-300° either with glycerin 
or ethylene glycol, starch, cellulose, epichlorhydrin, acetin, mannite, or other polyhydric alc. of 
fatty series. Or alk. salts of two compounds heated without free caustic or with caustic and 


lime. 
S. 874—‘Indigo.” 


644,326—Feb 27, 1900. R. Knietscu and H. §. A. Hort, Germany. (Badische.) 
Process of making indigo products. Piperazine deriv. for mfr. of indigo and homo- 
logs. 


4-Tolyl cLycocor carboxy diethyl ester, 2-naphthyl deriv., or other, heated with or without 
solvent and with or without 1-chlor NAPHTHALENE, or other, above 200°, product separated and 
fused with alkali to form leuco indigo. 

S. 874—‘Indigo.” 


646,841—Apr. 3, 1900. 
R. Knigetscu, H. S. A., Hott and E. Oxsperreit. (Badische.) 
Process of making aromatic isatin compounds. Isatin, homologs and analogs. 
INDOXYL or INDOXYLIC acid made as in 534,560, homologs or analozs, oxidized energetically 
in acid, neutral or alk. soln. by suitable imorganic agents. Isatin results directly without forming 


intermediate bodies, indigo, etc. 
S. 874—“Indigo.” 


647,263—Apr. 10, 1900. Bernhard HtymMann, Germany. (Elberfeld.) 
Ester of acetylphenylglycinortho carbonie acid. Acetyl phenyl glycin-2-carbonic 
acid, ethyl ester. 

Diethyl ester of phenyl GLYCIN 2-carbonic acid and acrety1 chloride, 1 mol. each, refluxed on 
water bath, excess chloride distilled off, residue washed with aq., dissolved in ether, and pptd. by 
ligroin. White crysts., sol. in ether, C,H, and alc., mixed wth dry caustic and heated at 100° 
yields leuco indigo. 

S. 874—“Indigo.” 


647,279—Apr. 10, 1900. Traugott SANDMEYER, Switzerland. (Geigy.) 
Proeess of making isatin. Isatin. 


HyprROxYLAMIN HCl, heated to go—-100° in aq. soln. with ANILIN, chloral hydrate slowly added, 
mixture made alk. and product pptd. by acetic acid as iso nitroso diphenyl ACETAMIDIN, which is 
condensed in H,SO, at 100-105° to ISATIN a-anilid, pptd. by carbonate, then boiled in dil. acid 
to split into anilin and isatin. 

S. 874—‘Indigo.” 


647,280—Apr. 10, 1900. T. SANDMEYER, Switzerland. (Geigy.) 
Process of producing indigo. Indigo, free of, or mixed with definite amounts of, in- 
dirubin. 


{satin a-anilid treated in alc. soln. with (NH,),S of 10 per cent H,S to produce indigo free 
of indirubin. Increasing proportions of isatin with isatin anilid gives shades varying from green 
blue to reddish violet, due to indirubin. A blue GREEN to red VIOLET vat dye. 

S. 874—‘“‘Indigo.”” Note 647,281 for mfr. of isatin-a-anilid. 


GROUP VII.—INDIGO AND INDIGOID 197 


647,281—Apr. 10, 1900. Traugott SANDMEYER, Switzerland. (Geigy.) 
Alpha-isatin anilid. JIsatin a-anilid for indigo mfr. 


Thio CARBANILID heated to 50—-60° with alk. cyanide and basic lead salt in aq. soln. with or 
without alc. to form hydrocyan carbo DIPHENYLIMID, which, with yellow (NH,),S forms diphenyl 
amino thio ACETAMIDIN. This when heated at 90-110° in conc. H,SO, yields isatin a-anilid, 
which forms dark violet needles m.p. 126°, easily sol. in warm alc. (YBr), turning blue with 
NaOH, easily sol. in ether, benzene and CS, (VR), and in org. or mineral acids (OR). 

S. 874—“Indigo.” Note 647,280 for conversion into indigo. 


651,453—June 12, 1900. 
D. Vortanner, H. S. A. Hott and H. WeissBprENNER, Germany. (Badische.) 
Process of making indoxyl bodies. Indoxyl, esters and sulfo derivs. 


Phenyl GLycoco, 2-carboxylic diethyl ester, converted into acetyl, formyl, benzoyl, or other 
deriv., and boiled with 20 per cent NaOH yields indoxyl or its esters. Other methods of con- 
densation to indoxyl and other alk. agents claimed. Products are non-cryst. or oily compounds 
sol. in most org. solvents, and may be sulfonated. 

S. 874—“Indigo.” 


657,539—Sept. 11, 1900. B. Heymann, A. Herre, Germany. (Elberfeld.) 
Monoacetyl-indoxyl and process of making same. N-Acetyl indoxyl. 


Diacetyl InpDoxyL made as in 618,096, pulverized, and heated in dil. alk. salt soln. at 70°. As 
the diacetyl comp. dissolves, the acetyl group attached to 3-carbonyl is split off, and the acetyl 
N-deriv., which is more difficultly saponified, crystallizes out. N-Acetyl indoxyl is a white cryst. 
powd., m.p. 135°, easily sol. boiling aq., in alc., dilk NaOH, and yields indigo with alk. oxidation. 

874—“‘Indigo.” 


661,871—Nov. 13, 1900. H. S. A. Hoxit, Germany. (Badische.) 
Process of making an indigo-leuco compound. Phenyl glycocol 2-carbo acid. 
ANTHRANILIC acid heated in powd. KOH at 150°, GLYCERIN carefully added and temp. raised 
to 220° until hydrogen ceases to evolve, then pptd. with acid. Mannite, cellulose, starch and 
other poly-hydroxy compounds of fatty series as well as glycerin claimed. I,euco indigo is formed 
by heating with caustic alk. or acetic anhyd. and sod. acetate, then saponifying. 
S$. 874—‘Indigo.”” Note 643,502. 


662,073—Nov. 20, 1900. J. Korrscuet, France. (Soc. Chim.) 
Indigo dye and process of making same. Methyl indigo, two isomers. 

3-TOLUYL aldehyde, nitrated, two mononitro products (of m.p. 44° and 64°) separated by frac. 
distn. in vacuum, each combined in alk. soln. with AcETONE to form the isomeric ketone, then com- 
bined with bisulfite, and oxidized in alk. soln. by air to form two isomeric methyl indigoes. Blue 


powds. insol. aq., alc., and acetone; BLUE vat dyes of redder shade than indigo. 
S. 888—“Indigo MLB.” 


662,074—Nov. 20, 1900. Joseph Kortscuet, France. (Soc. Chim.) 
Nitro toluylie aldehyde. Nitro toluyl-3-aldehyde. 

TOLUYL 3-ALDEHYDE in 10 parts 98 per cent sulfuric acid, heated to 40°, and 1 mol. dry 
NaNO, added, crude nitration product separated, washed with aq. containing alk. carbonate, frac- 
tionally distilled in vacuum and first two-thirds and last third of distillate separately treated. 
Product from last third forms crysts. (Y) m.p. 43-44°. Properties of compounds with amines, 
etc., show differences between this product and that of 662,075. 


662,075—Nov. 20, 1900. Joseph Korrscuet, France. (Soc. Chim.) 
Nitro toluylic aldehyde. Mono nitro toluyl-3-aldehyde. 
Same procedure, using ToLUyYL 3-aldehyde, as in 662,074, except that first two-thirds of dis- 


tillate is treated separately. This fraction is cryst. (m.p. 64°), and reacts differently with amins, 
as shown by patent. 


198 DIGEST OF PATENTS 


662,076—Nov. 20, 1900. Joseph Koertscuet, France. (Soc. Chim.) 
Acetone compound of nitro-meta-toluylic aldehyde. Acetone condensation 

product of nitro tolyl 3-aldehyde. ‘ 

Nitro ToLuyL 3-aldehyde, obtained as in 662,074, mixed with 1.6 parts acetone at O° and 
1% per cent NaOH added. Pure product m.p. 104° crysts. from ether, C,H,, and alc., when 
stirred in weak caustic soln. with air gives a violet BLUE. 

S. 874—“Indigo.” 


662,703—Nov. 27, 1900. August Stock, Germany. (Hdéchst.) 
Indoxyl derivatives and process of making same. Indoxyl methyl ketone for 
indigo mfr. 
ANTHRANILIC acid ethyl ester combined in benzene soln. with chlor acetone to form acetonyl 
ANTHRANILIC acid ethyl ether, which, with sod., forms 1npoxyLt methyl ketone. Indoxyl methyl 
ketone melts at 153°, is easily sol. in ether, alc., hot benzene, and caustic alk., diff. sol. in CHC1,, 


and forms indigo when heated with H,SO,, or with alk. and oxidized. 
S. 874—‘Indigo.” M. L. B. 


662,754—Nov. 27, 1900. Fritz Benner, Germany. (lLeonhardt.) 
Cyanmethyl-anthranilic acid and process of making same. Cyan methyl an- 
thranilic acid, alkyl ester. 

ANTHRANILIC acid in aq., alc., or dil. acetic soln., combined with KCN and FoRMALDEHYDE to 
form cyan methyl ANTHRANILIC acid, which is then alkylated. When heated with alc. and dehyd. 
agent, such as HCl or H,SO,, esters of phenyl glycocol 2-carbo acid are formed. 

S. 874—‘“Indigo.” Note 662,755. 


662,755—Nov. 27, 1900. Fritz Benper, Germany. (Leonhardt.) 
Process of making phenyl-glycocol-ortho-carboxylic acid. Phenyl glycocol 
2-carboxylic acid, or derivs. 

ANTHRANILIC acid HC] or derivs., mixed with solns. of KCN and ForMALDEHYDE to form 
cyan methyl ANTHRANILIC acid, which, with ETHYL bromide forms an ester. The derived acid 
amid is formed by dissolving in conc. H,SO,, and the thio amid by treating NH, soln. with yel- 
low (NH,).S. Products boiled in 30 per cent NaOH, then made acid, give desired glycocol. 

S. 874—‘“Indigo.” Addition to 662,754. 


669,794—Mar. 12, 1901. Benno Homoixa, Germany. (H6chst.) 
Process of making indigo. Indigo. 
2-Chlor BENzorc acid, 2 parts, or other halogen deriv., and 1 part GLycocoL, condensed by 


heating in alk. to 200° then oxidized in alk. or acid soln. 
S. 874—‘Indigo.”’ 


673,887—May 14, 1901. Julius OppeERMANN and August Ferre, Germany. (Kalle.) 
Process of making nitro and chlor benzaldehyde. 2-Nitro benzaldehyde. 


2-Nitro ToLvoL is chlorinated to form 2-nitro and 2-chlor BENzyL chloride, crude oil refluxed 
with dil. alcohol, sod. acetate and carbonate to first form and then saponify 2-nitro and 2-chlor 
benzyl acetate, alcohol distilled off, products crystallized or salted out and oxidized with mixed 
acid to 2-chlor and 2-nitro BENZALDEHYDES, the latter separated from accompanying 2-nitro TOLUOL 
by bisulfite and from each other partly by removing the solid nitro comp. by pressure then dis- 
tilling the liquid with steam to recover the 2-chlor deriv. 

S. 874—‘Indigo.” 


675,217—May 28, 1901. Benno Homo.ixka, Germany. (Hdéchst.) 
Process of making phenylglycin-ortho-carboxylic acid. Phenylglycin 2-car- 
boxylic acid. 

Salts of 2-chlor or brom BENzorIc acid and GLycocon in aq. soln., are evaporated in vacuum, 
dried at 100-120° and then further heated for some hours at 220°. Melt is dissolved in aq., soln. 
pptd. by acid, excess 2-chlor benzoic acid extracted from ppt. by CHCl,, and product purified by 
recryst. from dil. HCI. 

S. 874—‘Indigo.” 


GROUP VII.—INDIGO AND INDIGOID 199 


677,239—June 25, 1901. Rudolf Knietscu and Robert HotpMann, Germany. (Badische.) 
Halogen-substituted indigo and process of making same. _ 6.6’-Dichlor indigo 

and sulfo deriv. 

4-Chlor 2-nitro TOLUENE heated in sulfuric acid soln. with MnO, to 135-130° for 4-5 hours, 
the 4-chlor 2-nitro BENZALDEHYDE separated as the bisulfite comp. and condensed with AcETONE and 
alkali to 6.6’-dichlor indigo. A brown-red powd., with black streak, that sublimes, (VR) is sol. 
in boiling C,H,NO, or C,H,NH,, and insol. in common solvents; a violet RED vat dye, fast to 
washing and light, that may be sulfonated. 

Note 677,240 for sulfonated dye. 


677,240—June 25, 1901. Rudolf Knierscu and Robert HorpMann, Germany. (Badische.) 
Indigo sulfo-acid. Sulfonated 6.6’-dichlor indigo. 

Dye made as in 677,239, is sulfonated in 10 parts 5 per cent fuming H,SO, or in 5 parts 1o 
per cent fuming acid at 50°. The sulfo deriv. as free acid and salts, except with barium, is sol. 
in aq., contains chlorine, and dyes wool BLUE from acid bath. 

Note 677,239 for unsulf. form. 


680,395—Aug. 13, 1901. . Johannes PFLEGER, Germany. (Roessler.) 

Process of making indoxyl] derivatives. Indoxyl derivs. 

. Phenyl ctycocot, Na salt, homologs or derivs., added to fused mass of sodamid, with or 

without alk. cyanide or caustic alkali as diluent, at temps. varying from 180—230°, according to 

conditions. Or glycocol can be intimately mixed with sodamid and introduced little by little into 

a vessel heated at 250°. The NH, evolved excludes air. Method avoids use of esters of glycocol. 
S. 874—“Indigo.” 


690,332—Dec. 31, 1901. Daniel VorLANDER and Bruno DreEscHER, Germany. (Badische.) 
Acylated indoxylie acid and process of making same. Mono acetyl, propionyl, 
benzyl, or other indoxylic acid. 

InpoxyYLic acid alk. melt in aq. soln., nearly neut. with glac. acetic or other acid, and acETICc 
anhyd or acetyl chloride added in small portions, (heat hastens reaction) or the powd. alk. melt 
may be mixed with acetic anhyd., dry or in benzene soln., at 30-40°. Other acyl chlorides are 
claimed and separation from acet indoxyl given. Mono acet indoxylic acid crystallizes in leaflets, 
m.p. 125°, sol. in alk., alc. and ether, the alc. soln. turns red with FeCl,, alk. oxidization yields 
indigo. 

S. 874—“Indigo.”’ Note 546,165 for preparation of alk. melt, and 778,775 for acet indoxyl 
mfr, 


690,346—Dec. 31, 1901. Fritz BENDER, Germany. (Leonhardt.) 
Process of making acetyl-phenyl-glycocol-ortho-carboxylie acid. Acetyl 
phenyl glycocol 2-carbo acid. 
Phenyl ciycocot 2-carbo acid in aq. soln. as the neut, Na salt, or in presence of a salt 
that can act as an alkali, such as Na,CO, or NaC,H,0, treated with acetic anhyd. at common 
temp., and product pptd. by dil. H,SO,. 


697,545—Apr. 15, 1902. Traugott SANDMEYER, Switzerland. (Geigy.) 
Process of making indigo. Indigo. 

IsatT1In a-anilid in sulfuric acid soln., treated with alk. H,S to form a-thio isatin, which with 
alk. agents, strong or weak, containing H,S, forms indigo. a-Thio isatin as produced is a 
brownish gray ppt., sol. in alc. and ether (Br), is very unstable, sol. in alks. (B), from which 


soln. sulfur and indigo separate. 
S. 874—“‘Indigo.”” Note 647,279 and 647,281. 


698,328—Apr. 22, 1902. Paul Semper, Germany. (Badische,) 
Process of making indigo from indol. Indigo from indole. 


InpoLE in paste and Caro’s reagent (potassium persulfate and conc. H,SO, combined to 
form sulfo mono per acid), mixed at 0°, or, after making alk., at room temp. Sod. sulfite or 
bisulfite, together with air or oxygen, will also effect the change of indol to indigo. 


200 DIGEST OF PATENTS 


699,581—May 6, 1902. Paul Serpet, Germany. (Badische.) 
Indigo-diacetic acid and process of making same. _ Indoxyl diacetic acid, etc., 
to produce indigo or indigo diacetic. 

ANTHRANILIC acid condensed with 2 parts chlor acretic acid by heating in alk. carb. soln. 
at 80° to form ANTHRANILIC diacetic acid, which a) refluxed in 55 per cent NaOH gives In- 
DOXYL acetic acid, or b) heated with NaOH at 200° gives INpDoxyL carbo acid. When diluted 
and oxidized, both yield indigo diacetic, mono acetic, mono methyl or dimethyl indigo, or by 
treatment at 300° in NaOH-CaO, yield indigo. Indigo diacetic acid forms crystals, sol. in 
hot aq., in alc. and ether, decomp. by dry heat. 

S. 874—‘‘Indigo.”’ 


704,804—July 15, 1902. Benno HomouiKxa and Otto LiepKnEecut, Germany. (Hoéchst.) 
Process of making indoxyl. Indoxyl. 

Phenyl ciycin phenyl glycid, or homologs, heated to a high temp., 180-210°, with sodamid, 
with or without KCN, KOH or NaOH as diluent. The evolved NH, excludes air. 

S. 874—“Indigo.”’ 


706,921—Aug. 12, 1902. Moriz von Gators, Germany. (Héchst.) 
Process of making bromindigo. Brom indigo. 

Inpico white paste slowly mixed with bromine in requisite proportion, stirred until ab- 
sorption is complete, filt. washed and dried. Bromination and oxidation take place simul- 


taneously. 
Near S. 880 and 881—‘“‘Brom Indigo.’”’ Note that this patent is earlier than any brom in- 


digo recorded in Schulz. 


712,190—Oct. 28, 1902. Willibald Hentscuet, Germany. (von Heyden.) 
Process of making phenylglycin. Improved yield of phenyl glycin. 

One part chlor acetic acid refluxed 2 hours, with 3 parts ANILIN, preferably dil. with alc., aq., 
ether, esters, hydrocarbons, anilin, etc., alkali added and alc. and excess anilin expelled by 
steam. Phenylglycin is pptd. by HCl. One part anilin yields one and a half parts of glycin, 
or three times the usual yield. 

S. 874—‘‘Indigo.”’ 


712,793—Nov. 4, 1902. Benno Homo.xka and Friedrich von Bouizano, Germany. (Badische.) 
Process of making indoxyl. Indoxyl. 


Methyl AnTHRANILIC acid, alkali salt, or N-formyl or acetyl derivs. etc., fused at high temp. 
with sodamid diluted with hydroxide or cyanide of alk., in closed vessel without access of air 
till NH, is all evolved and the N hydrogen is substituted by an acid radical. 

S. 874—‘‘Indigo.”’ 


713,437—WNov. 11, 1902. Henry S. A. Hott, Germany. (Badische.) 


Substituted indoxyl and process of making same. Brom indoxyl for indigo or 
halogenated indigo. 

InDOXYL or INDOXYLIC acid acted upon by bromine, or other halogen, in neut. or acid soln. 
or suspension, to form brom indoxyl, which a) heated with HCl, sod. acetate, pyridin, anilin, 
b) or heated in aq. at high temp., c) or let stand moist at usual temp. d) ot treated in 
alk. soln. with FeCl,, is converted into brom indigo, while chlor and iod. derivs. yield indigo. 
Halogenated indoxyl derivs. are yellow substances, diff. sol. in aq. and acids, and easily con- 
verted to indigo both on and off the fiber, without oxidizing agents. 

Note 715,074 for indigo derived, and also 546,165. 


714,000—WNov. 18, 1902. Otto L1rEBKNECHT and Benno HomoiKxa, Germany. (Hoéchst.) 
Process of making indoxyl. Indoxyl and indigo. 

Phenyl ciycin, or other aromatic comp. containing the group R-N-CH,-CO, where R means 
C,H;, such as phenyl glycinyl PHENYL glycin, a-phenyl HYDANTOIN or diphenyl HYDANTOIN, etc., 
gradually added at 180-200° to melt of alkali metal or its alloy with heavy metal, alkali earth 
metal or their nitrides, carbides, or other substances adapted to decomp. aq., diluted with caustic 
or cyanide. 

S. 874—‘Indigo.” 


— 


GROUP VII.—INDIGO AND INDIGOID 201 


714,042—Nov. 18, 1902. 
Bruno R. Setrert, Curt Puitipp and Max H. Gmeriner, Germany. (von Heyden.) 


Process of making indigo and intermediate products. (Product also claimed.) 
Indoxylic acid esters and indigo. 


Dialkyl esters of nucleus substituted and nonsubstituted phenyl GiyciNn 2-carbo acids treated 
with nitrite in acetic acid soln. and resulting N-nitroso deriv. refluxed with alk. reducing agents, 
such as Na,S or (NH,),S excluding air (a), diluted and then oxidized. The pseudo indoxylic 
acid ester formed as an intermediate product at (a) separates as yellow green crysts., m. p. 
183°, insol. aq., alk. and alc., more sol. in glac. acetic, unchanged by acids, converted by alk. 
into indoxylic acid ester. 

S. 874—“‘Indigo.” 


715,074—Dec. 2, 1902. Henry S. A. Hout, Germany. (Badische.) 
Indigo color and process of making same. _ Indigo, brominated or not. 


InpoxyL or brom INDOXxYL together with 1npoxyL or other halogenated indoxyl, heated with 
(a) pyridin or other base, (>) sod. acetate in alc. soln., or with (c) air in alk. aq. soln. to 
form brom indigo. Chlor or iod indoxyl by same process yields nonhalogenated indigo. Brom 
indigo is a blue powd., sol. in cold C,H,NH, or CS,; a BLUE vat dye giving shades redder and 
more brilliant than indigo. Reactions of indigo and four brom indigoes are tabulated in patent. 
Near S. 879—‘“‘Brom indigo.” Note 713,437 for brom indoxyl. 


726,688—Apr. 28, 1903. Benno Homo.ixa, Germany. (Hochst.) 
Indigo mixture and process of making same. _ Indigo sulfo acid. 


2-Nitro BENZALDEHYDE, or other ortho nitro aromatic aldehyde and acrToner condensed in 
dil, alkali to form 2-nitro phenyl @-lactic acid methyl ketone, 2 mols. of which mixed thor- 
oughly with at least 1 mol. of benzyl aniLiIn sulfo, sod. salt, or salts of other benzylated ar- 
omatic bases, are sol. in aq. and when made alk. yield indigo sulfo. Products are easily sol. 
in hot aq. and are stable. 

Near 877—“‘Indigo sulfo acid.” 


7 27,270—May 5, 1903. Augustus BiscHLER, Switzerland. (Basle.) 
Process of making indoxyl. Indoxyl produced at low temp. 

Phenyl cGiycin, its carboxylic acid salts, or other, heated with 2 parts anhyd. KOH at 
200° and o.7 part Na,O added, or three ingredients may be mixed cold and gradually heated. 
The caustic acts as flux and oxide, being more powerful dehydrating agent, causes reaction to 


take place at lower temp. 
S. 874—‘“Indigo.” 


729,217—May 26, 1903. Arnold Rautyen, Germany. 
Process of making brom indigo. Mono or dihalogenated indigo. 

Indigo saturated with acids, organic or inorganic, or with CS,, to which 1 or 2 mols. bro- 
mine or chlorine in same solvent are added at moderate temp. Dibrom indigo has the appear- 
ance of indigo, soln. in H,SO, is yellow green, it sublimes, and may be sulfonated; it is a 
BLUE vat dye. 

S. 879—“Brom indigo.” Note 807,782 for similar dye by different and more detailed 
process. 


730,148—June 2, 1903. Paul EF. Oserreit, Germany. (Badische.) 
Indigo coloring-matter containing halogen and process of making same. 

Dibrom indigo. 

Phenyl ciycocot 2-carbo or cyan methyl ANTHRANILIC acid mono brominated in glac. acetic 
acid, (ligroin, benzene or other), separated, and product boiled with alk. then with acetic an- 
hyd. The latter solvent is distilled off in vacuum, residue saponified with NaOH and oxidized 
with air. Dibrom indigo resembles indigo, is insol. in cold glac. acetic, CS, CHCl,, and hot 
alc., contains bromin, and is a BLUE vat dye of slightly redder shade than indigo. 

Near S. 879—‘“‘Brom indigo.” Note 662,754. 


731,385—June 16, 1903. Paul E. Oserrert, Germany. (Badische.) 
Process of making indoxyl. Indoxyl and indoxylic acid with improved yield. 


Phenyl ciycin 2-carbo, disodium salt, in strong caustic alk. soln. evaporated dry in vacuum, 


202 _ DIGEST OF PATENTS 


then heated above 200°. Mixed alkalies may be used in melt. The expensive and tedious op- 
eration of grinding ingredients together is avoided, and decomp. of glycin by evaporation in air. 
S. 874—“Indigo.” 


737,836—Sept. 1, 1903. Willibald HentscHEL, Germany. (Heyden.) 
Process of making indoxyl and indigo preparations. Indoxyl and indigo with 
increased yield. ’ 


Phenyl ciycin, homologs or derivs. (esters, amids, anilids, etc.) heated with caustic alkalies 
and alk. alccholates, with or without alkali earths, to 100-250°, to form INDOXYL. 
S. 874—“Indigo.”’ 


746,965—Dec. 15, 1903 Rudolf KnigrscH and Henry S. A. Hout, Germany. (Badische.) 
Process of making indoxyl and derivatives thereof. Indoxyl and indigo. 


2-tolyl ctycin, K salt, or homologs, heated with 3 parts of an oxide of an alk. earth such 
as barium oxid at 290-300°. Strontium oxid gives less yield but both SrO and BaO produce 
more indoxyl than CaO. 

S. 874—“‘Indigo.” 


756,171—Mar. 20, 1904. 
Rudolf Knirrscu, Paul SrrpEL and Georg. W. Meisrer, Germany. (Badische» 


\ 


Process of making indoxyl and derivatives. Indoxyl. 


Phenyl ciycin, K salt or other, heated at 250° without air, with an alk. oxide such as sod. 
oxide dil. with NaOH, KOH, CaO, SrO, BaO, or mixtures of these. Free alkali metal must 
not be present. Caustic may be converted to oxide by electrolysis or the oxide may be obtained 
by heating Na with Na,O, or K with KOH, 

S. 874—“Indigo.”’ 


761,007—May 24, 1904. Paul E. Oxsrerreit, Germany. (Badische.) 
Chlorinated indigo and process of making same. __ 5.5'.7.7’-tetra chlor indigo, or 
di deriv. 


Phenyl ciycoco. 2-carbo or cyan methyl ANTHRANILIC acid, in glac. acetic, or other soln., 
to which 1 or 2 mols. chlorine are added. Anthranilic acid comp. then must be boiled in 15 
per cent NaOH. Resulting mono or dichlor phenyl GLycocoL 2-carboxylic acid separated, acet- 
ylated, acetic anhyd. recovered by distn. in vacuum, product saponified in dil. NaOH and 
oxidized by air. 

S. 885—‘‘Brill. Indigo.” BASF /B. Note 662,754. 


765,996—July 26, 1904. Albrecht Scumipt and Rudolf Mixier, Germany. (Héchst.) 
Manufacture of brominated indigo. (Product not claimed.) Brom indigo by elec- 
trolysis. 


Finely divided InpDIGO or indigo white mixed with HBr, 4o per cent, electrolyzed, with or 
without diaphragm, using carbon electrodes, current of 2.5 V. and 3 amp., to form mono or 
dibrom product according to amperage and time applied. Sulfuric acid, 20-80 per cent, con- 
taining HBr, may be used with a bromide present, or not. Strong acid solns. required. The 
composition of product is not known, but properties resemble those of brom indigo from dry 
bromination or by synthesis from indoxyl. A BLUE vat dye. 


768,455-—Aug. 23, 1904. Benno Homo.xa and Friedrich von Bowzano, Germany. (Hochst.) 
Glycollie acid anilid-orthocarboxylic acid and process of making indigo. 
Indigo. : 

ANTHRANILIC acid and GLYCOLLID fused together at 180—200° to form GLycoLic acid anilid 
2-carboxylic, Na salt, which fused in alkali at 240-300° yields leuco indigo. Glycolic acid an- 
ilid 2-carboxylic acid when purified forms colorless crysts., m.p. 167°, slightly sol. cold aq., very 
sol. hot aq., alc., ether and acetone. 

S. 874—‘Indigo.” 


772,560—Oct. 18, 1904. Sylvain Ercuwart, France. (Soc. Chim.) 
Printing compound of orthonitrophenyl lIactoketone. 2-Nitro phenyl lacto 
ketone compound for indigo dyeing. 


2-Nitro phenyl methyl LAcTO KETONE mixed with 3 parts 4-TOLUENE sulfo salt, or other ar- 
omatic or fatty sulfo acid or salt, or sulfonated oleic acid, Turkey red oil, esters thereof, etc. 


Se gg tne 


GROUP VII.—INDIGO AND INDIGOID 203 


For printing pastes a thickener is added. Print or dye material, dry, and pass through 15 per 
cent NaOH. 
S. 874—“Indigo.” 


772,775—Oct. 18, 1904. Wilhelm BEHAGHEL and Gustav C. Schumann, Germany. (Badische.) 
Process of making indoxylic compounds. Indoxylic compounds. 


Hydroxy ethyl ANILIN, or any aromatic amin containing a hydroxy ethyl group attached to 
the amino N, heated in autoclave at 280-290° with 3-4 parts caustic alkali. Lime sodium oxid, 
or sodamid may replace some of the caustic. 

S. 874—“Indigo.” 


776,884—Dec. 6, 1904. Augustus BiscHLER, Switzerland. (Basle.) 
Process of making indoxyl. &e. Indoxyl. 


Phenyl cGiycin, or other aryl glycin, salts, homologs, or derivs., heated to 250° in alkali 
melt containing some alkali metal (Na), then ANILIN, ammonia, acetylene or other agent to re- 
move H,O is introduced and heating continued till reaction is complete. 

S. 874—‘“‘Indigo.”? Addition to 761,440. 


778,725—Dec. 27, 1904. 
Daniel VorRLANDER, Bruno DrEescHER and Paul SemeLt, Germany. (Badische.) 
Aeylated indoxyl and process of making same, ' Acet-indoxyl. 


InpoxyL and 1npoxy.ic acid melt, or other, (from phenyl GLiycocoL 2-carbo acid and KOH) 
neut. with acid, then acetic anhyd., (benzoyl chloride, or other) added to form mono acetyl 
deriv., filt., and acet indoxyl separated from acet indoxylic acid by dissolving the latter in ice 
water. Acet indoxyl alone produced by boiling dil. alk. soln. of mixed melt and acetylating. 

S. 874—“Indigo.” Note 690,332 and 546,165. 


778,752—Dec. 27, 1904. 
Rudolf Knigerscu, Paul SerpEer and Otto J. Graut, Germany. (Badische.) 


Process of making indigo. Improved yield of indigo from phenyl glycocol and derivs. 


Improvement consists in conducting melt under substantially anhydrous conditions. A mix- 
ture of mol. NaOH and KOH, as near water-free as possible, to which an alkali earth oxide 
is added in excess of that sufficient to combine with all the water in the melt, (1 part CaO to 
3.6 parts alkali), is heated to 265° and phenyl cLycocot or deriv. added. Yield is about 50 
per cent of theory and becomes greater as amount. of water present is reduced by more alkali 
earth oxide, the amount of which is limited by the difficulty in stirring the melt. 

S. 874—“‘Indigo.” Note 617,652 and 622,139. 


798,077—Aug. 29, 1905. Paul SerpEL, Germany. (Badische.) 
Process of making indolic bodies. Indolic bodies as by-product in indigo mfr. 
Phenyl cLycin 2-carboxylic, or derivs., heated in alkali at 280-300° with or without re- 
ducing agents such as Fe powd. sulfites, etc., dild., oxidized, indigo removed by filtration, and 
indole recovered from soln. by ether, benzene by steam distn., or as picrate, etc. Higher temp. 
of melt and presence of reducing agents increase yield of indole. 
Addition to 794,049. 


807,782—Dec. 10, 1905. Albrecht Scumipt, Germany. (Héchst.) 
Process of brominating indigo. Brominated indigoes (mono, di, tri, etc.) with least 
formation of isatin. 

Indigo in inorganic acid soln., subjected to the action of 1 mol. Br at ro-15° till Br is 
absorbed then cooled to O° and filt. More Br, with or without carrier, gives higher bromina- 
tion. Br may be produced by electrolysis, with or without diaphragm. Liberated HBr may be 
recovered. Acid solvents may be H,SO,, HCl, HBr, HF or H,PO. Stronger H,SO, than 
78 per cent, or heat, results in sulfo indigo, while weaker acid than 50 per cent converts into 


bromisatin. 
S. 879—“‘Brom indigo Rathjen.” Note 729,217, for another process. 


812,598—Feb. 13, 1906. Albrecht ScHMipt and Erich Kronuouiz, Germany. (Hochst.) 
Process of chlorinating indigo. Chlorinated indigo. 


Inpico white, or indigo, containing some dry hydrosulfite N. F. mixed in CCl,, CS,, or 
similar solvent, treated with sulfuryl chloride in amounts according to chlorination desired. 


14 


204 DIGEST OF PATENTS 


a 


Gaseous SO,Cl, can be applied to dry indigo white or to this in solid solvents such as Na,SO, 
or FeSO, and carriers such as iodin may be used. 
Near S. 885—‘“‘Brill. Indigo.”” Note 807,782 for brom product. 


818,341—Apr. 17, 1906. 
Wilhelm BrHacuet and Gustav K. Schumann, Germany. (Badische.) 
Process of making phenylglycin salts. Phenyl glycin salt in improved yield. 


Chlor acetic acid with 5 parts ANILIN heated 3 hours at 100° temp., then aq. evaporated 
in vacuo at 120-140°, alk. carbonate or caustic added, excess anilin distd. over with steam, the 
phenyl crycin anilid separated, heated in an autoclave with one mol. caustic alk., the liberated 
anilin distd. off and soln. evapd. dry in vacuum. 


8$19,348—May 1, 1906. Paul FRIEDLAENDER, Germany. (Kalle.) 
Red sulfur dye and process of making same. ‘Thio indigo. 


Thio INDOXYL or its carboxylic acid dissolved in dil. alk. and treated with oxidizinz agents, 
as K,;Fe(CN),, air, Fe,Cl, or K,Cr,O, in acid soln. Thio indigo is a red powd., sublimes to 
form bronze colored needles, is diff. sol. in usual solvents; and is a fast RED vat dye. 

S. 912—‘“‘Thio indigo Red B.”’ 


823,294—June 12, 1906. Karl ScHIRMACHER, Germany. (Hdchst.) 


Vat-dye and process of making same. An indigo from the glycin of dianthranilic 
acid. 


DIANTHRANILIC acid and chlor acetic acid, Na salts, are refluxed in aq. soln., product sepd. 
and converted into Na salt by adding carbonate. The resulting glycin of DIANTHRANILIC acid, 
sod. salt, is heated in mixed KOH and NaOH melt in presence of a chemical capable of bind- 
ing water, to 270-280°, dild. and oxidized. Dyestuff is green-black powd., insol. in aq. and 
usual solvents, and sol. in conc. H,SO, (G); a fast GREEN vat dye. 


831,844—Sept. 25, 1906. Gadient Ener, Switzerland. (Basle.) 
Process of making a red vat-dyeing dye. Thio indigo. 


Saticy, thio acetic acid, refluxed for about 5 hours in 5 parts nitro benzene soln. or other 
aromatic nitrohydrocarbon. Diphenylamin or other indifferent solvent may be used with the 
nitro solvent. Dyestuff is violet red powd., insol. aq. and cold alc., slightly hot alec. (VR), more 
sol. in hot benzene (R, fluor), sol. conc. H,SO, (BG), pptd. on diln.; a violet RED vat dye, fast 
to washing, light and Cl. 

S. 912—“‘Thio indigo Red B.” 


836,309—Nov. 20, 1906. Gadient Ener, Switzerland. (Basle.) 
Red violet to violet-blue dye and process of making same. Thio indigo. 


Isatin a-arylids, such as IsATIN a-anilid, in acetic anhyd. or other solv., refluxed with sat- 
IcyL thio acetic, which forms thio 1npoxyL then combines with first component. Pure dyestuff 
consists of blue violet needles, sol. in conc. H,SO, (B), pptd. on diln., sol. in warm benzene 
(RV-BrR, fluor); red vioLetT to violet BLUE vat dye. 

S. 900. “Ciba Violet’? (non halogenated). Note 841,003 and 848,356 for halogenated dye 
and 848,355 for lower homolog. 


839,099—Dec. 25, 1906. Augustus BiscHuER, Germany. (Badische.) 


Process of making indoxyl, &c. Indoxyl homologs or derivs., with higher yield and 
less decomp. 


Fifteen parts Na and 4o parts K salt of phenyl cGiycin or other aryl glycin or derivs., 
added to 240 pts. NaOH at 250° and to parts abs. alc. as vapor introduced by means of cur- 
rent of hydrogen, heating being continued until indoxyl does not increase. Previous methods 
give low yields or impure product, (sodiamiiietal). Use of alc. considerably increases the yield, 

S. 874—‘Indigo.” tei ait 9 


~% 


841,003—Jan. 8, 1907. Gadient Ener, Switzerland. (Basle.) 
Yellow-red dye and process of making same. Thio indirubin. 


Thio sALIcyL acetic with 1saT1n or homologs in nitrobenzene soln., heated to 225-230° on 
oil bath for 2-3 hours. Orange red crysts., insol. in aq., diff. sol. hot alc., aniline and nitro- 


GROUP VII.—INDIGO AND INDIGOID 205 


benzene (Rt.), sol. hot benzene and chloroform (VR-fluor), sol. cold conc. H,SO, (Br) and 
hot (VR), pptd. on diln. (Br); an orange rep vat dye. 
S. 905—“‘Thio Indigo Scarlet.” 


841,456—Jan. 15, 1907. Robert ScHMiptin, Germany. (Hochst.) 
Process of making phenylglycin. Phenyl glycin or homologs. 

Sixty-two parts NITROBENZENE ‘or homolog, 100 parts ground cast iron and 7 parts ANILIN 
are heated to 70° in reflux app. and 47 parts chlor acetic acid in 100 parts aq. are gradually 
added, while keeping at boil. Temp. is kept at 98—-100° for two hours, mass neut. with Na,CO,, 
excess aniline distilled off, soln. filt., and phenyl glycin pptd. from conc. filt. by acid. 

S. 874—‘Indigo.” 


$48,354—Mar. 26, 1907. Gadient Encr, Switzerland. (Basle.) 
Halogenated red dye and process of making same. Dichlor thio indigo. 

4-Chlor or brom 2-amino BENzoIc, diazotized, and combined with thio cGiycotic acid to 
form chlor thio saLicyL acetic in which the halogen is in para position to the carboxylic group. 
In nitro benzene or other nitro-hydrocarbon soln. this is heated to 225-228°. Reddish cryst. 
powd., diff. sol. alc. ether and CHCI,, sol. warm C,H, (VR-fluor), sol. boiling C,H;NO, (R), 
in conc. H,SO, (G), in fuming H,SO, (R); an orange rep vat dye. 

S. 909—‘*Ciba Red B.”’ Note 831,844. 


848,355—Mar. 26, 1907. Gadient Enci, Switzerland. (Basle.) 
Red-halogen vat-dye and process of making same. Halogenated thio indirubin. 

Thio SALICYL acetic or thio indoxyl condensed with 1sarin, and product suspended in nitro- 
benzene or glacial acetic, slowly heated to a boil in reflux app. with bromine, chlorine, or with sub- © 
stances able to deliver up halogens. Brown to orange red cryst. powds., diff. sol. hot alc. and 
C,H,, easily sol. hot C,H,NO, (R), in conc. H,SO, (BrBk), in fuming H,SO, (RV), on diln. 
clear (BrR); a RED vat dye, faster to washing than a non-halogenated dye. 

S. 906—‘“‘Thio Indigo Scarlet, G.’? Note 841,003 for non-halogenated dye, 848,356 for an- 
ilid, and 836,309 for non-halogenated anilid. 


848,356—Mar. 26, 1907. Gadient Ene1, Switzerland. (Basle.) 
Red-violet to blue vat-dyes and process of making same. Halogenated mono 
thio indigo. 

Thio InpoxyL or thio salicyl acetic condensed with a-1sar1n anilid, or other alfa isatin ar- 
ylid, using nitrobenzene or other indifferent diluent, then heated gently with bromine or other 
halogen. Dyestuffs are sparingly sol. in alc. and hot C,H,, easily sol. in C,H;NO, (BV), soln. 
in conc. H,SO, or in fuming acid (B), unchanged by heating and pptd. on diln.; red vioLET to 
BLUE vat dyes. 

S. 900—“Ciba Violet 3 B.” Note 836,309 for non-halogenated dye, 954,273 for mono. hal. 
dye, and 848,355. 


850,444—Apr. 16, 1907. Arnold Rantyen and Carl StepnHan, Germany. (Rahtjen.) 
Process of making indigo. Indigo from isatin a-anilid. 

IsaTin a-anilid in alc., acetone or benzol soln., into which H,S is passed until colorless, di- 
luted and oxidized with air and alk., or simply heated. 

S. 874—‘Indigo.”’ 


8$50,827—Apr. 16, 1907. Paul FRIEDLAENDER, Germany. (Kalle.) 
Thio-indoxyl derivative and process of making same. Thio indoxyl and carbo 
deriv. (Leuco thio indigo.) 

Cutior acetic and thio satrcytic condensed to form thio saLicyt acetic acid, heated with 
NaOH at 160-250° or with acetic anhyd. at 50-80°, to thio 1npoxyL carbo, then heated or acid 
added to form thio Inpoxyt. Derivs. are claimed. Carboxyl group eliminated by heating with 
or without acids and by steaming. Products are diff. sol. aq., easily sol. alk., and form RED 
dyes when oxidized. 

S. 912—‘“‘Thio Indigo Red B.” 


856,687—June 11, 1907. Gadient Enc1, Switzerland. (Basle.) 
Tribromo derivatives of indigo and process of making same. _ Tribrom indigo. 

Inpico refluxed in nitrobenzene or 2-nitrotoluene soln., to which sufficient bromine is added 
to form tri-brom indigo; glacial acetic, or trichlor benzene or 2-nitro toluene also may be used 


206 DIGEST OF PATENTS 


as solvents. Dark blue to brownish violet powd., insol. aq., sol. hot aniline or nitrobenzene 
(B-Bv), sol. conc. H,SO, (GB), in fuming sulf. (B); a BLUE vat (GY) dye, fast to washing 
light and chlorine. 

S. 880—‘‘Helindon Blue BB.” Note 729,217, 807,782, 856,776 and 883,703 for other brom 
products. 


856,776—June 11, 1907. Gadient Enc1, Switzerland, (Basle.) 
Tetrabromo derivative of indigo and process of making same. ‘Tetra brom 
indigo. 


InpIGo or its mono-, di- or tri-brom substitution product brominated in nitrobenzene, or 
other soln. by refluxing at 225° for 1.5 hours or allowing to stand at room temp. 3-4 hrs., 
then refluxing at 130-135°. Blue to blue-violet powds., insol. aq., diff. sol. hot chloroform, 
aniline or nitrobenzene (B-BV), sol. conc. H,SO, (B); BLuE vat (Yt) dye, fast to washing, 
light, chlorine. 


S. 881—“‘Dianthrene Blue BB.” Note 916,217 and also 883,703 for modified process. 


860,900—July 23, 1907. Nikodem Caro, Germany. (Cianamide.) 
Process of making indigo. Larger yields of indigo. 

Phenyl Guycin, derivs. or salts, added to hot melt (350-400°) consisting of disodium cy- 
anamid, 1 part, with sodium cyanide, 5 parts, as an inert flux of low melting pt., cooled, diluted 
and oxidized by air to produce dye. 


S. 874—“Indigo.” 


867,305—Oct. 1, 1907. Karl ScHIRMACHER and Bernhard Deicke, Germany. (Hdéchst.) 
Vat-dyestuff. 6.6’-Dialkoxy thio indigo. 

3-Amino 4-CRESOL is acetylated then ethylated to form acetyl 3-amino 4-cresol ethyl ether, 
oxidized (KMnO,) to 4-ethoxy acetyl ANTHRANILIC acid, separated by acid, saponified in NaOH 
soln. and diazotized. Diazo soln. treated with alk. xantHocENic acid then alk. chlor AcETIC 
to produce 4-ethoxy thio saLicyL acetic acid which, heated in NaOH to 180-200° yields 4- 
ethoxy thio NAPHTHENE carbo. Oxidation in alk. soln. (ferricyanide) produced dye. Methyl 
deriv. also claimed. Orange red powds. insol. aq., slightly sol. hot alc., C,H,, acetic and 
CHCl, (OR), sol. conc. H,SO, (VB), heated with HCl splits off alkyl chlorides; an orange 
RED vat (Y) dye. 

S. 913—‘‘Helindon Orange R.” 


867,306—Oct. 1, 1907. Karl ScHIRMACHER and Richard Letopotp, Germany. (Ho6chst.) 
Vat-dyestuff. Diethyl 6.6’-dithio thio indigo. 

3-Nitro 4-AcETOLUIDIN (NH, = 1), oxidized and reduced to give 4-acetamino ANTHRANILIC, 
diazotized, potass. xanthogenate added in alk. soln., then heated with alk. chlor acetic at 100° 
for 3 hours, and the 4-acet amino 2-thio SaLIcyL acetic pptd. by acid. Separated product 
is saponified, diazotized, potass. xanthogenate again added in alk. soln. to form 4-xanthogenyl 
thio salicyl acetic, which is pptd. by acid, then refluxed with caustic and sod. ethyl sulfate to 
yield alkyl-4-thionyl thio salicyl acEric, which, pptd. by acid, heated again in caustic at 180— 
190° gives alkyl 4-thionyl oxythio naphthene carbo acid. This will yield on oxidation in alk. 
soln. (ferricyanide) a thio indigo. Red powds., insol. aq., slightly sol. hot alc., acetic, C,H, 
and CHCl, (OR), in conc. H,SO, (GB), heated with HCl splits off alkyl chloride; an alizarin 
RED vat (Y) dye. 

S. 916—‘‘Helindon Scarlet S’’ 


867,679—Oct. 8, 1907. Albrecht Scumipt and Wilhelm Bertram, Germany. (Hochst.) 
Red-violet dye and process of making same. Tetra chlor thio indigo. 

2-ACETTOLUIDIN dichlorinated, oxidized (KMnO,) to dichlor acet ANTHRANILIC acid, hydro- 
lyzed, diazotized, transformed into dichlor thio saLicyLic acid, or its di- or tri-thio carbonic 
acid ester, then by means of chlor acrETic in alk. soln. changed to 3.5-dichlor phenyl thio cLy- 
COLLIC 2-carbo acid. Heating with 4o per cent bisulfite at 150° under pressure or in acetic 
acid, forms dye. Brom comp. also claimed. Violet black powds., diff. sol. conc. H,SO, (G), 
in hot C,H,NO, (RV); red vioLeT vat (Y) dyes. 


| 


GROUP VII.—INDIGO AND INDIGOID 207 


867,714—Oct. 8, 1907. Gadient Enc1, Switzerland. (Basle.) 
Process of making a halogenated red dye. Halogenated thio indirubin. 

Thio INDOXYL (a-oxy thio naphthene) or salicyl thio acetic condensed with rsatIN, hal- 
ogenated with mixed conc. HNO, and HCl and pptd. by diln. A rep vat dye of same prop- 
erties as 848,355. i 

S. 906—“Thio Indigo Scarlet G.” Note 867,715 for isomer and 848,355, 887,609 for hal- 
ogenated dyes by other processes. 


867,715—Oct. 8, 1907. Gadient Enc1, Switzerland. (Basle.) 
Halogenated red vat-dye and process of making same. Dibrom thio indigo. 

Thio InDIGO (from sALicyL thio acetic heated in soln. of nitrobenzene or other nitro hy- 
drocarbon) brominated at 130-135° by refluxing with bromine, also in nitrobenzene soln. 
Other halogen compounds claimed. A gray violet cryst. powd., sol. conc. H,SO, (BG), pptd. 
on diln. (RV), diff. sol. hot C,H, (VR), easily sol. hot C,H;NO, (VR-Y flour); a violet rep 
wat (Yt) dye. 

S. 915—“Ciba Bordeaux B.” Note 851,844, isomer 848,354 (S. 909) and 867,714. 


761,440—May 31, 1904. Augustus BiscHLER, Switzerland. (Basle.) 
Process of making indoxyl, &e. Increased yield of indoxyl, homologs and derivs. 
PHENYL glycin sodium salt, or other aryl glycins or derivs., and caustic alkali heated in 
alkali melt at 230° then to 260°. Melt is formed from metallic Na, in dry KOH, with or 
without a little reducing substance such as sodium sulfite, in absolute alc. distilled in vacuum 
on oil bath until all alc. is removed. 
S. 874—“‘Indigo.”’? Note 776,884. 


868,294—Oct. 15, 1907. Robert ScHMipLIN, Germany. (Hdéchst.) 
Process of producing phenyl glycin and its homologues. Phenyl glycin and 
homologs. 


Chlor acetic acid and ANILIN or other primary base are refluxed in a suspension of freshly 
pptd. ferrous hydrate in a satd. soln. of NaCl or other indifferent alk. salt. The ferrous hy- 
drate is prepared from ferrous chloride or carbonate soln. to which sufficient NaOH or Na,CO, is 
added, followed by alkali salt to saturation and heating to 90-100°. Phenyl glycin iron salt formed 
is decomp. by NaOH or Na,CO,, anilin distilled off, iron removed by filtration and glycin pptd. 
by acid. 

S. 874—“Indigo.” 


868,295—Oct. 15, 1907. Albrecht Scumipt, Germany. (Hochst.) 
Vat-dye and process of making same. Thio indigo and halogen derivs. 

Phenyl thio GLycocot 2-carbo (salicyl thio acetic) the tolyl, chlor phenyl or other aryl or 
halogen aryl deriv., heated with 6 parts bisulfite to 150-190° under pressure. Claims same 
dye as is produced by alk. fusion. Red powd., sol. conc. H,SO, (dark YG), in hot C,H,NO, 
(VR), giving red streak on porcelain; a violet RED to orange RED vat dye. 

S. 912—“*Thio Indigo Red B.”’ 


868,755—Oct. 22, 1907. Hans Beart, England 

Process of making indigo, &e. Improvement in yields of indoxyl and indigo. 
Phenyl ciycin 2-carbo, di sodium salt, refluxed dry with ANILIN and metallic sodium 

(sodium anilid) or other aryl sodamid, or mitxures of sodamid with aryl amins, or other glycins. 
S. 874—“‘Indigo.” 


872,085—Nov. 26, 1907. Albrecht Scumipt, Germany. (Hoéchst.) 
Brown vwat-dye. Acet-s-amino thio indoxyl-2-carboxylic or leuco 6.6’-diamino thio indigo. 

Acet 4-amino ANTHRANILIC acid, diazotized, treated in alk. carb. soln. with XANTHOGENIC 
acid, then chlor acetic acid to form acet 5-amino thio salicyl acetic acid, which is condensed 
in alkali then oxidized in neut. or faintly alk. soln. with ferric salts. Brown powd., insol. in 
aq., alk. or dil. acids, sol. conc. H,SO, (B), diff. sol. in C,H;NO, (OBr); a BRown vat dye. 

Isomer of S. 927—‘‘Helindon Gray 2B.” Note 872,585 for hal. dye, 872,086 and 959,617 
for isomers. 


208 DIGEST OF PATENTS 


872,086—Nov. 26, 1907. Albrecht Scumipt, Germany. (Hochst.) 
Green-black wat dye. Acet.-5-amino thio naphthene indoxyl carbo or leuco 5.5’-diamino 
thio indigo. 

Acet. 5-amino ANTHRANILIC acid treated by same process as 872,085, with amino group in 
para, not meta, position to the sulfur. A black powd., insol. aq., caustic, dil. acids, alc., ether, 
or benzene, sol. conc. H,SO, (dark GB); a green BLacK vat (YG) dye. 

Isomer of S. 921—‘‘Helindon Gray 2B.”’ Note 872,085 and 959,617 for 3.3’ and 2.2’ iso- 
mers and 872,585 for hal. dye. 


872,115—Nov. 26, 1907. Gadient Ene1, Switzerland. (Basle.) 
Mixed chlorobromo derivatives of indigo and process of making: same. 

Mixed mono or dichlor, mono, di, or tri brom indigo. 

Mono or di-chlor INDIGO, suspended in nitrobenzene or other indifferent medium, di- or 
tri-brominated at 225-228°. Blue to violet powds., insol. aq., somewhat sol. hot C,H,NH, or 
C,H,NO, (B-V), sol. fuming H,SO, (B-V); vioLeT to BLUE vat (Yt) dyes, fast to washing, 
chlorine and light. 

Near S. 884 or 887—‘“‘Brilliant Indigo.”? This patent apparently antedates S. 884 or 887 
(1911) by four years. 


872,227—Nov. 26, 1907. Gadient Enc1, Switzerland. (Basle.) 


Green vat-dye and process of making same. Halogen-1.2-naphthindigoes, or di- 
brom 1.2-naphthindigo. 


I.2-NAPHTHISATIN, brominated, refluxed with POCI,, containing PCI, added to 1o per cent 
HI in glac. acetic, boiled, cooled, and poured into aq. SO, or NH,SH and alc., made alk., di- 
luted and oxidized by air. Other halogen derivs. claimed. Dark green cryst. powds., sol. conc. 
H,SO, (GB), easily sol. hot C,H,NO, (GB); vivid GREEN vat (RBr) dyes, fast to washing, 
light, and chlorine. 

S. 891—‘‘Ciba Green G.”’ 


872,280—Nov. 26, 1907. Gadient Ene1, Switzerland. (Basle.) 
Monochloromonobromo derivatives of indigo and process of making same. 

Brom chlor indigo. 

Inp1co, mono-chlorinated in nitrobenzene soln. suspended in C,H.NO,, refluxed with a little 
more than two atomic proportions of bromine at 226° on oil bath for 2 hours. A blue cryst. 
powd., sol. conc. H,SO, (YG-BG), sol. fuming H,SO, (B), nearly insol. alc. and C,H,, some- 
what sol. hot C,H, NH, (GB) and hot C,H,NO, (B); a violet BLUE vat (Y) dye fast to washing, 
chlorine and light. 


872,585—Dec. 3, 1907. Albrecht Scumipt and Carl Prerzerr, Germany. (Hochst.) 
Orange vat-dye and process of making same. _ 5.5/-Dibrom 6.6/-diamino tho indigo. 
Acetyl 4-amino thio sALIcyL acetic, heated with alkali, leuco body oxidized to thio in- 
digo then chlorinated or brominated in nitrobenzene, chlorbenzene, glac. acetic acid, or other 
diluent. Brown powds., insol. aq., alk., dil. acids, alc., acetone, diff. sol. hot C,H,NO, (OBr), 
sol. conc. H,SO, (B); oRANGE vat dye, fast. 
S. 914—‘‘Helindon Orange B.’”? Note 963,813 for ethoxy deriv. 


874,649—Dec. 24, 1907. Karl ALBrEcHT, Germany. (Kalle.) 
Thio-indoxyl derivatives and process of making same. ‘Thio indirubin. 


Thio InDOxYL (a-oxy thio naphthene) or its carboxylic acid in hot alk. aq., condensed with 
ISATIN. Scarlet red needles, insol. or diff. sol. usual solvents, sol. conc. H,SO, (Br); an orange 
RED vat dye, fast to all agents. 

S. 905—‘“‘Thio Indigo Scarlet R.’? Note patent apparently duplicates 841,003 issued nearly 
12 months earlier to Engi, Basle. 


876,158—Jan. 7, 1908. * Gadient Enc1, Switzerland. (Basle.) 
Vat dye derived from indirubin and process of making same. [Di, tetra or poly 
brom indirubin. 

INDIRUBIN, from INDOXYL and ISATIN, refluxed in nitrobenzene for 3-4 hours at 130-140° 
with two or more atomic proportions of bromine. Violet cryst. powds., sol. conc. H,SO, (GB- 
G), sol. hot C,H,NH, and C,H,NO, (V); vioLtET vat (Y) dyes, fast to washing and chlorine. 

S. 897—“Ciba Heliotrope D.” 


GROUP VII.—INDIGO AND INDIGOID 209 


876,839—Jan. 14, 1908. Rudolf Pummerer, Germany. (Badische.) 
Red dye and process of making same. Thio indirubin, homologs and derivs. 


2.3-Diketo dihydro thio NAPHTHENE (thio ISATIN), homologs or derivs, condensed with 3- 
oxy thio NAPHTHENE (thioindoxyl), or other aryl thio glycolic acid or ortho carboxyl derivs., 
by heating at 140° with exclusion of air, with or without diluents such as C,,H,, C,H,NO, or 
C,H,,OH and with or without a condensing agent such as (CH,CO),O, ZnCl,, CaCl, or min- 
eral acid. Products may be sulfonated. Violet to brown red powds., sol. in C,H, (V-YR), sol. 
conc. H,SO, (Br-G); BLUE to RED vat dyes or in sulfonated form blue vioLET to brown-RED 
acid dyes. 


877,702—Jan. 28, 1908. Ernst Bryx, Germany. (Hochst.) 
Process of making arylthioglycollic-orthocarboxylic acids. Phenyl thio gly- 
colic 2-carbo acid, or other aryl derivs. 
ANTHRANILIC acid diazotized, soln. neut. with Na,CO, and at o-10° allowed to run slowly 
into an excess of Na,S soln., chlor acetic acid, Na salt, and NaOH added, heated for one 
hour at 100° and pptd. by acid. 


877,743—Jan. 28, 1908. Albrecht ScHmMiprt and Ernst Bryx, Germany. (Hochst.) 
Violet dye and process of making same. _5.5’/-Dimethyl thio indigo and homologs or 
derivs. 


ps-CumipIn, chlor toluidin or other amin, substituted in para position, but not in one 
ortho position, diazotized, condensed with xANTHOGENIC acid, then with chlor acetic in alk. 
soln. to form a para substituted aryl thio glycolic acid, which is heated gently with several parts 
H,SO,, monohydrate or 66°. Accelerators such as bisulfate, pyrosulfate, boric or phosphoric 
acids, chlorides, aromatic sulfo acids, or sulfur, increase yields. By regulating quantity and 
strength of sulfuric acid, and temp. and time of heating, an unsulfonated condensed di- or 
poly-alkyl thio-indigo results. Dyes are insol. aq., alk., dil. acids, sol. hot C,H,;NO, (RV), sol. 
conc. H,SO, (G); blue vioLer vat dyes. 

Near S. 912—‘‘Thio Indigo Red B.” 


881,157—Mar. 10, 1908. Karl ScHIRMACHER and Richard Leoporp, Germany. (Ho6chst.) 
Dark-green-black dye. Methyl or ethyl 5-thio indoxyl or leuco dimethyl or diethyl 5.5/-di- 
thio thio indigo and homologs. : 

Acet 5-amino ANTHRANILIC acid diazotized, combined in alk. soln. with xANTHOGENIC acid, 
then warmed in alk. soln. with chlor acEtic to form acet 5-amino thio SALICYL ACETIC, which 
is separated, hydrolyzed, diazotized, again combined with xanthogenic acid, refluxed in alk. 
soln. with METHYL or ETHYL sulfate, heated with NaOH to 180-190° to close ring, and finally 
oxidized to dye by alk. ferricyanide. Dark green black powds., insol. aq., sol. in alc. glac. 
acetic, C,H, and CHCl, (V), in conc. H,SO, (BG); black crrEN vat (Y) dyes. 

Thio isomer of S. 913—‘“‘Helindon Orange R.”’ 


881,158—Mar. 10, 1908. Karl ScuriRMACHER and Bernhard Deicke, Germany. (Hochst.) 
Dark-blue-violet dye.  5.5’/-Dimethoxy or diethoxy thio indigo. 

4-Amino PHENOL 5-carbo, acetylated, alkylated in alk. soln. with pIMETHYL sulfate, or other, 
to form 4-acetyl amino ANisoL 5-carbo, which is saponified, diazotized, condensed with xanTHo- 
GENIC acid then with chlor acetic, pptd., fused in alkali to close the ring, and oxidized. Dark 
violet powds., insol. aq., sol. hot alc., glac. acetic, C,H, and CHCl, (V), in conc. H,SO, (G); 
blue vioLeET vat (Y) dyes. 

Isomer of S. 813—‘‘Helindon Orange R.”’ 


881,159—Mar. 10, 1908. Karl ScuIRMACHER and Arnold Brunner, Germany. (Héchst.) 
Red vat-dye. (Product.) 4.4’-.6.6’-Tetra methyl thio indigo. 

6-Nitro 4.2-xYLIpINn diazotized, nitrile form, d by CuSO, and KCN, hydrolized in acid soln., 
the resulting 6-nitro 4.2-xyLIc acid reduced, ‘diazotized and condensed with xANTHOGENIC acid 
in alk. soln. then with chlor acetic acid to form 4.6-dimethyl thio salicyl acetic, which is con- 
densed in alkali to 4.6 dimethyl oxy thio naphthene carbo and oxidized with alk. ferricyanide. 
Red powd., insol. in aq., very diff. sol. hot alc., more sol. hot C,H,, glac. acetic and CHCISCR); 
sol. conc. H,SO, (G); a pale rep fast vat (Y) dye. 

Note 881,624 for similar dye by slightly different process, 


210 DIGEST OF PATENTS 


881,624—Mar. 10, 1908. Albrecht Scumipt and Ernst Bryx, Germany. (Héchst.) 
Making vat-dyestuffs. (Product claimed.) Tetra- to hexamethyl thio indigo, or other. 


2.4-XYLIDIN, 2.4.5-cumidin, or similar amin, diazotized and combined with XxANTHOGENIC 
then with chlor acetic acid to form 2.4-xylyl thio GLyconic acid, or other para methyl substi- 
tuted aryl thio glycolic acid, such that one hydrogen in ortho position to the sulfur is not 
substituted,_-which is condensed in chlor sulfonic soln. Violet powds., insol. in aq., alk., dil. 
mineral acids, sol. conc. H,SO, (G), in hot C,H;NO, (RV); blue vio.er vat dyes. 

Note 811,159 for similar dye. 


$83,703—Apr. 7, 1908. Gadient Ener, Switzerland. (Basle.) 
Process of making dibromindigo. Dibrom indigo. 


INDIGO in nitrobenzene soln. to which a theoretically sufficient amount of bromine, 4 atoms, 
is added to form dibrom indigo, heated to 225—-228° for 1.5 hours. Process adds 37.5 per cent 
Br as compared with 33 per cent by former methods. Deep blue cryst. powd., a violet BLUE 
vat (Y) dye, more intense and faster than indigo to washing and chlorine. 

S. 880—‘‘Helindon Blue BB.” Note 729,217, 807,782, 856,687, 856,776. 


887,609—May 12, 1908. Gadient Enc1, Switzerland, (Basle.) 
Red halogen wat-dye and process of making same. Halogenated thio indirubin. 


IsaTin, brominated in glacial acetic soln. to mono or dibrom isatin, or other halogen deriv., 
boiled in nitrobenzene, or other solvent, with 3-oxy thio naphthene, from sAticyLic thio acetic, 
using a condensing agent such as acetic anhyd. Dyes are slightly sol. in hot C,H, or C,H,;NO, 
(Rose-R), sol. conc. H,SO, (dull Br); RED vat (Y) dyes, fast to washing, light, and chlorine. 

S. 906—“Thio Indigo Scarlet G.”’ Note 867,714 and 848,355, etc., which employ different 
processes to obtain halogenated dyes, and also 841,003. 


888,230—May 109, 1908. Gadient Ener, Switzerland. (Basle.) 
Process of making monobromo indigo. Brom indigo. 


INDIGO in nitrobenzene soln., refluxed 1.5-2 hours at 225-228° with sufficient bromine (2 
atoms) to form mono brom dye. Dye contains theoretical amount of bromine, 24 per cent. A 
blue cryst. powd., giving a sLuE vat (Y) dye faster to washing and chlorine than mono brom 
deriv. Indigo R. 

Near S. 880—Helindon Blue BB.” Note 856,687 and 856,776. 


$91,690—June 23, 1908. Armin Gros, Switzerland. (Basle.) 
Red vat-dye and process of making same. Thio indole acenapthene indigo. 


Phenyl thio GLiycoco, 2-carboxylic, or 3-oxy thio naphthene, and ACENAPHTHENE quinone, 
heated dry to 230—250° or refluxed with sodium acetate in acetic anhyd., or alc. soln. Dye may be 
sulfonated. It is sol. in hot glac. acetic and hot C,H,, sparingly sol. in alc., sol. conc. H,SO, (G); 
an orange RED vat (V) dye. 

S. 907—“Ciba Scarlet G.’”’ 


888,852—May 26, 1908. Karl ScuirMACHER and Arnold Brunner, Germany. (Hodchst.) 
Brown vat dye. 


I-NAPHTHYLAMIN 2-sulfo diazotized, changed by CuSO, and KCN to 1-cyan NAPHTHALENE 2- 
sulfo, then by PCI, and POC, to 1-cyan naphthyl 2-sulfo chloride, which is treated with dil. 
H,SO, and Zn dust, separated and heated in alk. chlor acrrTic, resulting naphthalene 2-thio 
glycolic 1-carbo acid heated at 180-190° in NaOH, to oxy thio PHRENTHRENE carbo acid, or fur- 
ther saponified to oxy thio PHRENTHRENE. Latter comps., oxidized in alk. soln., form dye. 
Properties of purified intermediates are given. Brown powd., insol. aq. and alk., sol. in hot 
alc., CH cet, 


891,708—June 23, 1908. Hans Lasuarpt, Germany. (Badische.) 
Process of producing indoxylic compounds. Indoxyl compounds. 


Acetyl phenyl ciyc1n homologs, analogs and derivs., dry and finely powdered, mixed with 1-4 
parts freshly prepared, finely ground aluminum chloride, heated to 220-250° in a closed vessel 
in vacuo, in atmosphere of hydrogen, nitrogen, CO, or other indifferent gas, cooled, added to 
boiling dil. NaOH to saponify then oxidized by air. Other aluminum halides and acylated aryl 
glycins claimed. 

S. 874—“Indigo.” 


GROUP VII.—INDIGO AND INDIGOID 2I1 


hot 


892,897—July 7, 1908. Karl ScHIRMACHER and Hermann Lanpers, Germany. (Hochst.) 
Red vat dye. 4-Methyl 6-chlor thio indoxyl or leuco 4.4’-dimethyl 6.6’-dichlor thio indigo. 

4-Chlor 6-nitro 2-roLuyLic acid, reduced with Na,S to an amin, diazctized, then combined 
in alk. soln. with xANTHOGENIc and chlor acetic acids to form 4-methyl 6-chlor thio salicyl acetic 
acid, which when heated with alkali to 180-190° and prtd. by acid forms 4-methyl 6-chlor oxy 
thio naphthene carbo acid. Alk. oxidation gives dye. Dyes are red powds., insol. aq., alc., ether, 
sol. in hot C,H,NO, and glac. acetic (R), in H,SO, (G); a pale RED vat (Y) dye. 

S. g10—‘Helindon Blue, BN.” 


894,004—July 21, 1908. Benno Homo.ka and Richard Wepre, Germany. (Hochst.) 
Process of making alpha-oxythionaphthenes. Thio indigo from a-oxy thio naph- 
thene, homologs or carboxyl derivs. 
Methyl thio saticytic acid, methyl ester, heated with about equal parts alk. alcoholate and 
4 to 6 parts molecular mixture of NaOH and KOH, at 150 to 200°, to form a-oxy thio NAPH- 
THENS. Other condensing agents may be used, such as dialk. dicyanamid, amalgams or alloys, alk. 
alcoholates, alk. earths, metals, etc. Products are RED to VIOLET vat dyes. 


S. 912—‘Thio indigo Red S.’”’ Note 894,005. 


894,005—July 21, 1908. Benno Homo.ika and Richard We.pe, Germany. (Hochst.) 
Process of making sulfurized dyes. C,,H,S,0,. 

a-Oxy thio NAPHTHONES or a-oxy thio NAPHTHENE carbo acids heated at roo—130° in closed 
vessel with 10 parts cryst. Na,S,0,. Red cryst. powds., insol. aq., sol. conc. sulf. (G), in CHCl, 
(R), reduced by alk. agents; RED reducing sulfide vat dyes. 

S. 912—‘*Thio Indigo Red B.” Addition to 894,004. 


894,006—July 21, 1908. Benno Homo.xka and Richard WeE.tpEe, Germany. (Hoéchst.) 
Sulfurous leuco body and process of making same. _ Leuco thio indigoes. 

a-Oxy thio NAPHTHENES, or carboxyl derivs., heated with to parts cryst. sod. thiosulfate (6 
aq.) or other soluble thiosulfate and 10-15 parts comm’! GLYCERIN in closed vessel to temp. above 
100°. Leuco body is colorless, little sol. in aq., readily sol. in alc., wood alc., acetone and 
dil. alk., not fusible without decomp., alk. soln. exposed to air ppts. REpD, BLUE, VIOLET to red 
BROWN vat dyes. 


Near S. g912—‘‘Thio Indigo Red B.”’ 


§$94,149—July 21, 1908. Georges Imsert, Germany, 
Process of producing glycin derivatives. Phenyl glycin and derivs. 

Dichlor ethoxy ETHYLENE or dibrom deriv., 1 mol., prepared as in 894,148 (see Intermediates) 
refluxed with 3 mols. ANILIN or other aromatic amin in aq. or dil. alc. soln. with or without 


HCl, or heated at 150° in an autoclave. The excess halogen salt of aromatic amin may be re- 
covered. 


894,579—July 28, 1908. Augustus BiscHLEeR, Switzerland. (Basle.) 
Process of making indoxyl, &c. Indoxyl or leuco indigo. 


ANILIN, or other amin, added to a heated mixture of NaOH and Na, followed by PHENYL 
glycin, or other, and heating continued at 225-235° until 1npoxyL is formed. Difficulty caused 
by foaming from evolved hydrogen, in processes where the glycin is first added then the amin, 
is avoided by reversing this order. 


S. 876—‘“Indigo White.” Note 776,884. 


898,452—Sept. 15, 1908. Gadient Enc and Jaroslav Frouiicu, Switzerland. (Basle.) 
Vat-dye from indirubin and process of making same. as-Dibrom indirubin, or 
other dihalogen deriv. 

InpoxyL, phenyl glycin, methyl indoxyl or derivs., boiled with dibrom 1satin, or other dihalo- 
gen isatin (see list) in alk. soln. Brown red powds., sol. conc. H,SO, (dull BrV-V), sol. fuming 
H,SO,, 24 per cent (V), sparingly sol. hot C,H,, more sol. hot C,H,NO, (V); a pale vioLEeT vat 
(Yt) dye, fast to washing and chlorine. 

Near S. 897—‘‘Ciba Heliotrope B.” 


212 DIGEST OF PATENTS 


898,738—Sept. 15, 1908. Benno Homorixka, Germany. (Ho6chst.) 
Oxid of thioindigo dyes. Thio indigo oxide, C,,.-H,0,5,, and derivs. (constitution not 
given). 


Thio INDIGO or substituted thio indigo oxidized by strong agents such as HNO,, CrO,-H,SO,, 
etc. Red cryst. powd., insol. aq., ether and ligroin, sol. in boiling CHCl, and xylene (R), in 
conc, H,SO, (RV), in dil. caustic or neut. sulfite (OY), latter soln. when heated with dil. mineral 
acids yields red ppt., which can be produced on the textile fiber; fast RED vat dye. 


889,152—Sept. 22, 1908. Wilhelm Baver, Germany. (Bayer.) 
Process of making red vat-dyes. 6.6’-Dihalogenated thio indigo, or other. 

4-Chlor phenyl thio Giyco1ic acid or other halogenated aryl glycolic acid, mixed with chlor 
sulfonic acid (free from sulfuryl chloride but containing some moisture) keeping temp. low. Red 
powds., bronzy luster, sol. conc. H,SO, (YG); a RED vat (Y) dye. 

Near S. go09—‘“‘Ciba Red B.” 


899,863—Sept. 29, 1908. Gadient Ener and Herman Krart, Switzerland. (Basle.) 
Trichlorindigo and process of making same. Improvement in process for tri- 
halogenated indigo. 

Inp1co, treated in nitrobenzene, or other aromatic nitro hydrocarbon solution, with Cl gas 
aided by SbCl, or other halogen carrier to trichlor indigo. A violet bronze powd., insol. aq., diff. 
sol. CHCl, and C,H,, more easily sol. in hot C,H,NO, (VB), sol. in conc. H,SO,(GB); a BLUE 
vat (Yt) dye, fast to washing, light and chlorine. 

Note 915,338. 


899,994—Sept. 29, 1908. Hermann Kraft and Gadient Enc1, Switzerland. (Basle.) 
Violet vat dye and process of making same. Brom thio indigo, or other. 

NITROBENZENE condensed with 3-oxy thio NAPHTHENE in alc. soln., form the a-anilid of thio 
ISATIN, (2.3-diketo dihydro thio naphthene) or other alpha arylid, then boiled 3 hours together 
with ACETINDOXYL or indoxyl and Na,CO, in alcohol or nitrobenzene soln. and violet cryst. product 
separated, suspended in nitrobenzene, heated in oil bath at 220-230° and bromine added. Dark 
violet powds., sol. conc. H,SO,(B-GB), in hot C,H,NO,(V); vIoLET to violet BLUE vat (BrY) dyes, 
fast to washing, light and chlorine. 

Near S. 906—‘‘Thio Indigo Scarlet G.” 


904,867—Nov. 24, 1908. Armin Gros, Switzerland. (Basle.) 
Violet vat dyestuff and process of making same. Acenaphthene indigo. 
ACENAPHTHENE quinone condensed by heating in 90 per cent alc. soln. with INDoxyYL, adding 
trace of piperidin or calcined soda to ppt. dye, while hot. Dye is sol. in conc. H,SO,(G), diff. 
sol. hot alc. (BV), more easily sol. hot C,H,(RV); a vioLEeT vat dye. 
Near S. 907—‘‘Ciba Scarlet G.”? Note 891,690 for thio dye of same form. 


906,029—Mar. 23, 1900. Albrecht ScHmMipt and Ernst Bryx, Germany. (Héchst.) 
Red-violet dye and process of making same. _ 5.5/-Dichlor dimethyl thio indigo, or 
homologs. 


Chlor tolyl thio ciycocor acid (from 4-chlor 2-toluidin xANTHOGENIC and chlor AcETIC acids) 
or other aryl thio glycolic acid with halogen in para position and one ortho position free, heated 
at 100° with conc. sulfuric acid, then poured into aq. List of substituted amins possible to use 
(8) is given with color and reaction of dyes. Dyes are insol. in aq., alk. and dil. acids, sol. hot 
C,H,;NO,(VR), in conc. H,SO,(G); red vioLeT to violet RED dyes. 

S. 917—‘“‘Helindon Red B.” 


910,839—Jan. 26, 1900. Eduard Mitncu, Germany. (Badische.) 
Process of making thioindigo leuco compounds. Leuco thio indigo compounds (3- 

oxy thio naphthene carbo acids). 

w-Dichlor vinyl thio saticyLic acid (from thio saticyuic acid and trihalogen ETHYLENE) heated 
in mixed caustic and carbonated alkali to 125-150° then at 200-210°, dissolved and pptd. by HCl. 
Boiling in sod. alcoholate gives same product. Rep vat dye. 

S. 912—“‘Thioindigo Red.” 


ae ae Oe a 


| 


GROUP VII.—INDIGO AND INDIGOID 213 


815,338—Mar. 16, 1909. Gadient Enc1, Switzerland. (Basle.) 
Mono-brom-trichlor indigo and process of making same. Mono brom ttrichlor 
indigo. 


Trichlor InDIGO made as in 899,863, suspended in nitrobenzene, is mixed with bromin and 
refluxed at 220-230°. Small violet brown coppery crysts., sol. conc. H,SO,(B), in fuming sulf. 
(GB), in hot C,H,NH,(B), in C,H,NO, (BV); a violet BLUE vat (Y) dye, fast to washing, light 
and chlorine. 

Addition to 899,863. 


915,346—Mar. 16, 19009. Armin Gros, Switzerland. (Basle.) 
Vat dye and process of making same. Halogenated thioindole acenaphthene indigo. 


4-Chlor thio sALIcyL acetic acid and finely powd. ACENAPHTHENE quinone are heated to- 
gether at 220-250° or heated in an indifferent solvent like naphthalene, or in acetic anhyd. and 
dry sod. acetate. Other halogens and substituents claimed. 3-Oxy-thio naphthene is formed during 
the process. 

Near S. 908—‘“‘Ciba Red R.” Note 891,690, 904,867 and 965,170. 


916,030—Mar. 23, 1909. Albrecht Scumipt and Ernst Bryx, Germany. (Hochst.) 
Vat dye and process of making same. _ 7.7’-Dichlor thio indigo or other substituted 

7.7'-dihalogen thio indigoes. 

2-Chlor phenyl thio GLycotic acid from (2-chlor ANILIN diazotized and condensed with xan- 
THOGENIC and chlor acetic acid) added to cHLORSULFONIC acid with or without boric acid as 
accelerator, keeping temp. low. List of examples of other halogen aryl thio glycolic acids that 
may be used is given with colors produced on fiber. Dyes are insol. aq., alk., dil. acids, ligroin, 
alc. and ether, sol. hot C,H,NO, (VR), in cold conc. H,SO,(G), pptd. on diln.; RED VIOLET to 
BLUE vat (Y) dyes. 

S. 916—‘“‘Helindon Red B.” and 917 ‘“‘Helindon Red 3B.” Addition to 916,029. 


916,031—Mar. 23, 1909. Albrecht ScuMipT, Germany. (Hoéchst.) 
Highly-brominated indigoes and process of making same. Highly brominated 
leuco indigo, with at least two atoms bromine in excess of tetrahalogen indigo. 


Dibrom INDIGO mixed with an excess of liquid bromine, with or without solvent such as 
CCl, CS, etc., and with or without a bromine carrier such as iodine or POCI,, to form a green- 
black unstable highly brominated product which loses bromine with heat or with hydrosulfite, 
etc., to form leuco dye. Products are green-black, insol. in aq. and in CCl,, sol. in alk. hydrate 
and dyeing wool and cotton BLUE from these solns. 

Note 918,920. 


$18,820—Apr. 20, 1909. 
Albrecht ScuMipt, Heinrich RossnErR and Hans Batyorn, Germany. (Hoéchst.) 
Highly-brominated halogen indigoes and process of making same. _ Highly 
halogenated indigo, containing at least five atoms of halogen. 


Dibrom 1npIGo gently heated to 20—-40° in 85 per cent sulfuric acid to which a large excess 
(more than 5 atoms) of bromine is added. ‘The green black mass loses bromine in aq. or bi- 
sulfite soln., turns blue and forms tribrom (45 per cent) leuco indigo. Higher temp. in sulfuric 
acid treatment gives tetra brom (55 per cent) product. Other halogen derivs. and homologs 
claimed. Products are sol. in much conc. H,SO,(BrG) and in alk. hydrosulfite soln. yield BLUE 
vat (gray G) dyes. 

Addition to 916,031. 


920,156—May 4, 1909. Emil Kraus, Germany. (Cassella, N. Y.) 
Brominated indigo sulfid and process of making same. Halogen derivs. of 
indigo sulfid containing one atom S to two mols. indigo. 


InDIGO, in nitrobenzene or other diluent, to which is added bromine in same solvent, then 
sublimed sulfur and mixture allowed to stand, then heated to 120° and finally to 160-200°. Dark 
blue powds., almost insol. in alc., C,H,, CHCl, sol. in boiling C,H;NO, and C,,H,(GB), in conc. 
H.,SO,(BG), in 20 per cent oleum (sky B); a BLUE vat (Y) dye. 


923,959—June 8, 1909. Gadient Enc1, Switzerland. (Basle.) 
Red vat dye and process of making same. _ dAcetyl thio indirubin. 


Acetyl 1sat1n and 3-oxy thio NAPHTHENE or derivs., boiled together in alcohol, or the oxy 
thio naphthene can be produced in the reaction mass by heating thio salicyl acetic acid with a ‘ 


214 DIGEST OF PATENTS 


condensing agent (nitrohydrocarbon) and acetyl isatin. Products are diff. sol. cold alc. and C,H,, 
more sol. hot C,H, and C,H,NO,, sol. conc. H,SO, (dull Br); rep vat (Yt) dyes, fast to washing, 
light, and chlorine. 

Near S. 905—‘‘Thio Indigo Scarlet.”” Note 841,003, 848,355, 874,649 and 887,609. 


932,334—Aug. 23, 1909. Albrecht Scumipt and Robert Voss, Germany. (Hoéchst.) 
Brominated beta-naphthylindigo. (Process claimed.) Brom naphthyl indigo and 

higher brominated indigoes. 

2-Naphthyl rnp1co is suspended in CCl, and bromine added at low temp., product filtered and 
purified by bisulfite, alcohol, etc. Or 2-naphthyl indigo is refluxed in CCl, with sufficient bromine 
to form dibrom indigo (2 mols.) or is mixed at O° with liquid bromine, stirred for two days 
and diluted with CCl,, etc., to form higher brominated derivs. Dark green powds., sol. in conc. 
H,SO, (VB-B-BV), diff. sol. in usual solvents, somewhat sol. in C,H;NO, and C,H.NH,; fast 
GREEN vat dyes. 

S. 892—‘‘Helindon Green G.”’ 


937,040—Oct. 19, 1909. Wilhelm Baver and Alfred Herre, Germany. (Bayer.) 
Tribromindigo and process of making same. Tribrom indigo. 


Inpico, finely powdered, dissolved in cooled conc. sulfuric acid, bromine, HBr, or NaBr, 


slowly added, gently heated to 30° and added to aq. containing some bisulfite. Less than theoreti- 
cal amount of bromine may be used as HBr is decomp. by conc. sulfuric. Cooling the H,SO, 
prevents sulfonation. Violet blue powd., sol. conc. H,SO, (GB), sol. hot glac. acetic, phenol 
and benzaldehyde (B), on oxidation gives brom isatin m. p. 215; a green BLUE vat (Y) dye. 

S. 881—‘‘Dianthrene Blue 2R.” Schulz places this with the tetra brom product, while 
patent expressly states tri brom. See also 856,776, 937,041. (Tetrabrom). 


937,041—Oct. 19, 1909. ' Wilhelm Bauer and Alfred Herre, Germany. (Bayer.) 
Tetrabromindigo and process of making same. _ Tetrabrom indigo 

Inp1Go, finely powdered, added to conc. sulfuric acid, cooled to prevent sulfonation, bromine 
or other halogen slowly added and the whole heated to 45° then poured into aq. containing some 
bisulfite. Patent differs from 937,040 only in using sufficient bromine for the tetra brom deriv. 
instead of tri brom. Violet blue powd., sol. conc. H,S0O, (GB), sol. glac. acetic, phenol and 
benzaldehyde (B), oxidized gives brom isatin, m.p. 215°; a green BLUE vat (Y) dye. 

S. 88:1—‘‘Dianthrene Blue 2B.” Note 856,776, 916,217 and 937,040. 


937,194—Oct. 19, 1909. Carl StepHan and Arnold Rantyen, Germany. 
Process of making sulfurous-acid compound of alpha-isatin anilid. Sul- 
furous acid compounds of a-isatin anilid and homologs. 

Diphenyl oxALAMIDIN thio amid, or homolog, dissolved in hot dil. sulfuric to form soln. of 
ISATIN a-anilid, which is poured into aq. containing SO,, one mol., or its equivalent as bisulfite 
sulfite or thio sulfate salt. Only slightly acid soln. is required. 

S. 874—‘Indigo.” 


940,586—Nov. 16, 1909. Gadient Enc1 and Hans Kapreier, Switzerland. (Basle.) 
Brown vat dye and process of making same. Halogenated diamino indigo. 

4.4’-Diamino INDIGO one part, mixed with 15 parts bromine for 48 hours at ordinary temp. 
then diluted by CCl,, or it may be heated with 1 part Br 2-3 hours at 110-120°, or with 1 part 
Br. it may be stirred in 66° sulfuric acid at or below O° for 12-15 hours. Other solvents, such as 
glac. acetic or di and tri chlor benzene may be used and halogen carrier employed. Brown powds. 
sol. in conc. H,SO, and oleum (B), in hot C,H,NO, (Br); red Brown vat dyes. 


941,152—Nov. 23, 1909. Hermann Krart, Switzerland. (Basle.) 
Vat dye and process of making same. Halogen thio naphth-indigo. 

Brom b-NAPHTHYLAMIN chloride, from brom b-naphthisatin and PCl,, and 3-oxy thio NAPH- 
THENE, boiled in xylene soln. Dibrom derivs., halogen salts, and alfa as well as beta naphthisatin 
may be used in nitrobenzene, xylene or other solvent. Brown-red powds., sol. conc. H,SO, 


(G-GB), in hot C,H,NO, (R-V); brown VIOLET, gray VIOLET to vioiet BLACK vat dyes, fast to 
washing, light and chlorine. 


' 
f 
‘ 
‘ 


GROUP VII.—INDIGO AND INDIGOID 215 


943,560—Dec. 14, 1909. Eduard Mincu, Germany. (Badische.) 


Thiosalicylic compound and process of making same. Ethylene (‘acetylene’) 
bis thio salicylic acid for thio indigo mfr. 


Thio SALICyLIc acid, dipotassium salt, its sulfur or halogen derivs. or esters, and dichlor 
ETHYLENE or other symmetrical dihalogen acetylene in alc. soln. containing a little KOH, refluxed 
at 100°. Sulfo cyan benzoic acid may be used and anthracene o-sulfoxy carbo acid also. 

S. 912—““Thio Indigo Red.” Note 943,561 . 


943,561—Dec. 14, 19009. Eduard Mitncu, Germany. (Badische.) 


Thiosalicylic compound and process of making same. w-Dihalogen vinyl thio 
salicylic acid for thio indigo. 


Thio saticyiic acid, homologs, analogs and derivs., refluxed in alc. KOH with trichlor etuy- 
LENE, and pptd. with acid. Process and components the same as 943,560 except trichlor ethylene 
is used instead of dichlor ethylene. Colorless or slightly colored crysts., easily sol. in alc. or 


C,H,, more diff. sol. in ligroin, insol. in aq., alk. condensing agents give leuco thio indigo colors. 
S. 913—‘*Thio Indigo Red.” 


$43,678—Dec. 21, 19009. Benno HomoiKa and Robert WeEtp£, Germany. (Hochst.) 
Leuco bedy containing sulfur and process of making same. Leuco thio indi- 
rubin. 


Drox1NDOLE (by reduction of IsATIn with Zn and HCl) or derivs., mixed in aq. with a-oxy 
thio naphthene or its carbo acid, with or without -acid or alkali carbonate as an accelerator. 
White or reddish cryst. powds., slightly sol. aq., sol. in alc., acetone and dil. alk., the alk. soln. 
on exposure to air or other oxidizing agent deposits an insol. thio indirubin dye. 

S. 905—‘“‘Thio Indigo Scarlet R” etc. 


947,030—Jan. 18, 1910. Albrecht Scumipt and Ernst Bryx, Germany (Hochst.) 
Vat dye and process of making same. Amino 5.5/-dichlor-7.7’-dimethyl thio indigo. 

Thio rnpi1co, chlor or methyl derivs. or other, nitrated in absence of aq. and reduced or not 
or halogenated or not. Nitro group when present as such is reduced in the dye vat. Violet to 
dark powds., insol. in aq., dil. alk. and acids, ligroin, alc. and ether, sol. conc. H,SO, (G-GB); 


VIOLET to violet GRAY to BLACK vat dyes. 
Near S. g10—‘‘Helindone Rose BN.” 


948,241—Feb. 1, 1910. 
Paul E. Oserreit, Viktor VitzicerR and Paul Nawrasky, Germany. (Badische.) 

Halogenated indigo and process of making. = 5.5’-Dibrom-7.7’-dichlor indigo. 

4-Brom 6-chlor phenyl GiycIN 2-carbo, methyl ester (from phenyl glycin carbo acid, chlor- 
inated, brominated, then methylated), condensed in alc. soln. containing metallic sodium as con- 
densing agent to 5-brom 7-chlor indoxyl carbo acid ester, which when saponified and oxidized in 
alk. soln. forms a tetra halogen indigo. Dye is sol. in’ boiling dimethyl anilin, in conc. H,SO, (B), 
when oxidized by mixed acid gives 3-chlor 5-brom isatoic acid, (m.p. 260°); a BLUE vat dye. 

Near S. 884—‘‘Brilliant Indigo 2B.” 


949,592—Feb. 15, 1910. Eduard Miincu, Germany. (Badische.) 
Process of making a thioindigo dye. Sulfonated thio indigo red. 


Ethylene (‘‘Acetylene’’) bis thio saticyLtic acid or derivs. obtained as in 943,560 added 
rapidly to eight parts chlor sulfonic acid at 25-35°. Fuming sulfuric acid, trichlor-benzene with 
P.0., or other acid condensing agent may be used and diluting agent or flux may be present. 
Sulfuric acid as solvent produces a sulfonic acid or not according to temp. and speed of reaction. 
Rep to violet RED vat dyes or in sulfonated form violet RED acid dyes. 

Sulfonated S. 912—‘‘Thio Indigo Red B.” Addition to 943,560. 


954,273—Apr. 5, 1910. , Gadient Enc1, Switzerland. (Basle.) 

Process of making fast-gray prints. (Product not claimed.) ‘Treatment of fibers 
dyed or printed with mono halogen, mono thio indigo. 

; Fiber dyed, or printed with brom mono thio 1np1Go, from 3-oxy thio naphthene (thio indoxyl) 

and 1saTINn a-anilid, treated at 90° with hot water with or without soda or soap, alkali, acid, neu- 


216 DIGEST OF PATENTS 


tral or acid salt, bichromate, etc., gives fast GRAY prints and dyeings, greenish in artificial light. 
Dyes may be used in combination with other dyes. 
S. 8099—‘‘Ciba Gray G.” Note 848,355 and 848,356. 


955,410—Apr. 19, 1910. 
Paul Juxius, Viktor V1ILLIGER and Paul NawiAsxy, Germany. (Badische.) 
Tetrachlor-indigo and process of making same. _  4.4/-5.5’-Tetrachlor indigo. 


3-4-Dichlor phenyl GLycIN 2-carbo acid methylated, condensed in alc. soln. with sodium to 
4.5-dichlor INDOxYL carboxylic acid ester, saponified with alkali and oxidized. Green blue powd., 
sol. conc. H,SO, and hot dimethyl aniline (B), oxidized with HNO, gives 4.5-dichlor isatin m.p. 
247°; a green BLUE vat dye, fast to washing, light and chlorine, and unchanged in artificial light. 
S. 886—‘‘Brilliant Indigo G.”’ 


955,699—Apr. 19, 1910. Albrecht Scumint and Karl Turrss, Germany. (Hoéchst.) 
Thioindigo vat dye. (Process also claimed.) Brom toluidino thio indigo, or other halo- 
gen nitrogen indigoes. 


Thio 1npIco, brominated in presence of SO,Cl, to penta or tetra brom product, then heated 
to 120-170°, with amins such as TOLUIDIN, anilin, or 30 per cent ammonia, with or without BEN- 
ZENE or other solvent and preferably with sodium acetate and copper powder to assist replacement 
of halogen by amin. Blue violet to blue powds., sol. conc. H,SO, and hot C,H,NO, BV-B), 
almost insol. in alc., C,H,, CCl,; fast violet BLUE to BLUE vat dyes. 

Near S. 903 or 904—‘‘Helindon Brown.” 


957,683—May 10, 1910. 
Paul Jutius, Viktor VitLicErR and Paul Nawzasxy, Germany. (Badische.) 

Dichlor-dibrom-indigo and process of making same. = 4.4'-Dichlor-5.5/-dibrom 

indigo or 4.4’-dibrom-s.5’-dichlor indigo. 

3-Chlor 4-brom phenyl Giycin 2-carbo acid, or 3-brom 4-chlor deriv., methylated in alc. sodium 
and condensed in acetic acid soln. to 4-chlor 5-brom 1nroxyL carbo ester which is saponified with 
alkali then oxidized. A green blue powd., sol. conc. H,SO, and dimethyl aniline (B); green BLuE 
vat dyes, fast to washing, light and chlorine, and shade unchanged by artificial light 

S. 887—Brilliant Indigo 4 G.” 


958,464—May 17, 1910. Wilhelm Bauer and Alfred Herre, Germany. (Bayer.) 
Blue wat dye. A dihalogenated 2-indoxyl 4-brom 1-naphthol. 


Dibrom ISATIN, or other halogen or methyl substituted isatin, converted into chloride by PCI, 
in dry benzene soln. then added to 4-brom 1-NAPHTHOL in same solvent. The oxygen of the alfa 
beta group in the isatin may be replaced by easily replaceable substituents other than Cl, such as 
other halogens, sulfur, NH,, alkoxy, etc. Blue cryst. powds. with metallic luster, sol. hot 
C,H,NO, (B) in conc. H,SO, (GB); BLUE vat (Y) dyes, especially fast to Cl. 

Near S. 985—‘‘Halogen-Alizarin Indigo 3 R.”’ Note 958,465 and for non halogenated dye, 
999,439. 


958,465—May 17, 1910. Wilhelm Bauer and Alfred Herre, Germany. (Bayer.) 
Blue wat dye. Same constitution as 958,464 with Cl for Br in naphthol rest. 


Dibrom ISATIN, or other, in dry benzene soln. converted to chloride by PCl, then mixed with 
soln. of 4-chlor 1-NAPHTHOL, also in dry benzene. Dark blue cryst. powds., of coppery luster, sol. 
hot C,H, or C,H.NO, (B), in conc. H,SO, (GB); siug vat (Y) dyes, especially fast to Cl. 

Near 894—‘‘Halogen-Alizarin Indigo 3R.” Note 958,464 and 999,439 for non halogenated dye. 


Oa 


959,617—May 31, 1910. Albrecht Scumipt and Ernst Bryx, Germany. (Héchst.) 
Vat dye and process of making. 7.7’-Diamino thio indigo or its 5.5’-dichlor deriv. 
2-Nitro phenyl thio Giyconic acid or halogen derivs. condensed with SO,Cl, to 7.7/-dinitro thio 
INDIGO, or derivs., then reduced with Na,S with or without sulfur present, or ‘with other reducing 
agents. Black to dark blue powds., insol. in aq., alk., dil. acid or alk., sol. conc. H,SO, (B), diff. 
sol. hot C,H.NO, (VBr-V); dark BLUE to BLACK vat dyes. 
S. 921—‘‘Helindon Gray 2B.” 


a ae ae ee ed 


960,098—May 31, 1910. : Hermann Krart, Switzerland. (Basle.) 
Green vat dye and process of making same. Brom b-naphthindol indigo. 


Brom b-NAPHTHISATIN Chloride, or other, and INDOXYL or ACETINDOXYL, heated in dry alcohol 
soln. with dry anhyd. Na,CO;. Dye may be further brominated in nitrobenzene by heating to 


GROUP VII.—INDIGO AND INDIGOID my 


100-120° with Br, giving dye of hluer shade and faster to washing and Cl. Green black powds., 
sol. conc. H,SO, (G); GREEN vat (O) dyes fast to washing, light and chlorine. 
Note: One half the molecule is like S. 891—‘“‘Ciba Green G.”’ 


960,671—June 7, 1910. Martin Mucpan and Willy Herrmann, Germany. (Cons. Elek.) 
Process of making indoxyl, &c. Indoxyl or leuco indigo. 
Phenyl GLYcIN potassium, or other aryl glycin, mixed with Ca-Si alloy, or other, added to 


caustic melt at 220-250°. Indoxyl may be isolated as such or oxidized at once to indigo. 
S. 874—“Indigo.” 


961,396—June 14, 1910. Wilhelm Bauer and Alfred Hrerrt, Germany. (Bayer.) 
Vat dye. a-Anthrol dibrom indole, homologs and other halogen derivs. 

IsaTin, treated with PCl, in benzene soln. to form chloride, added to a-AntTHROL, also in dry 
benzene, or acetic anhyd. soln. Dibrom isatin and other isatin derivs. in which the oxygen of 
the alfa keto group is replaced by easily replaceable substituents, halogen, sulfur, NH,, alkoxy, etc., 
and anthrol or other comps. having a free ortho position to the hydroxy group are claimed. Dye- 
stuffs are dark blue cryst. powds., sol. hot C,H,NO, (B), in conc. H,SO, (BrG); BLuE to green 
BLUE vat (OY) dyes, especially fast to Cl. 

S. 893—‘‘Alizarin Indigo O.’’ Note 999,439 (Elbel and Wray) which employs naphthol 


instead of anthrol. Also 961,397, 961,398, 961,399, 980,140, 998,596, 1,001,919, 1,005,140, 
1O05,141, 1,101,778. 


961,397—June 14, 1910. Wilhelm Bauer and Alfred Herre, Germany. (Bayer.) 
Vat dyestuff. Dibrom indole-naphthol. 

Dibrom 1saT1N, converted to chloride by PCl., then combined with 1-NaPHTHOL in dry benzene 
soln. Other substituted isatin derivs. containing halogen in the nucleus and in which the oxygen 
of the alfa keto group is replaced by easily replaceable substituents such as halogen, S, NH,, 
alkoxy, etc., are claimed. Dark blue cryst. powd., sol. hot C,H,NO, (B); BLUE vat dyes, fast to 
chlorine. 

S. 895—‘‘Alizarin Indigo 3 R.” Addition to 961,396. 


$61,398—June 14, 1910. Wilhelm Bauer and Alfred Herre, Germany. (Bayer.) 
Blue dye. Dibrom indole-4-methoxy naphthol. 

7-Methyl 1saT1n, converted to chloride by PCl,, then combined with 4-ethoxy NAPHTHOL in 
dry benzene. Same general claims as 961,396 and 961,397. Dark blue cryst. powds., sol. hot 
C,H,NO, (B); violet BLUE vat (Y) dyes, especially fast to Cl. 

Near S. 895—‘“‘Alizarin Indigo 3 R.” 


961,399—June 14, 1910. Wilhelm Bauer and Alfred Herre, Germany. (Bayer.) 
Blue dye. Dibrom indole-4-ethoxy naphthol. 
Dibrom 1saTIN, converted to chloride by PCl,, then combined with 4-ethoxy NAPHTHOL in dry 


benzene. Same claims as 961,396 et seq., and same properties for dyes. Buiur vat dyes, fast 
to Cl. 
Near S. 895—‘‘Alizarin Indigo 3 R.” 


963,377—July 5, 1910. Otto LigEBKNECHT, Germany. (Roessler.) 
Manufacture of indigo leuco bodies. Indoxyl or leuco indigo, homologs and derivs. 
Phenyl ciycin, K salt, heated in alkali melt with alkali metal (Na) and ammonia (alkali amid 
formed in situ). Aromatic comps. capable of forming indigo leuco bodies in an alkali melt are 
claimed, together with use of alkali metal in melt and addition of NH, to form an alkali amid 
which eliminates water from the mass. Brive vat dyes. 
S. 874—“Indigo.” 


963,813—July 12, 1910. Albrecht Scumipt and Ernst Bryx, Germany. . (Hochst.) 
Red halogenized dye and process of making. MHalogenated 6.6’-diethoxy thio 
indigo. 


6.6’-Diethoxy thio 1np1co allowed to stand or gently heated with halogen or SO,Cl,, diluted 
with CCl,, or C,H,NO,, etc., and separated by filtration. Other 4-oxy ethers of this indigo or 


218 DIGEST OF PATENTS 


their leuco comps. are claimed, with use of low temps. Dyes are insol. in aq., dil. acids, or alk., 
alc. and ether, sol. in hot C,H,NO, (OR) in conc. H,SO, (B); fast RED vat (Y) dyes. 


Near S. 914—‘“‘Helindon Orange D.” Addition to 872,585 and 812,508. 


965,170—July 26, 1910. Karl Exper, Germany. (Kalle.) 
Process of condensing reduction products of acenaphthene-quinone, &c. 

(Product also claimed.) Leuco thio indol hydro acenaphthene indigo. 

ACENAPHTHENE quinone ground with alcohol then slowly added to Fe in dil. acetic acid, 
warmed to 80-90°, filt., purified and refluxed with 3-oxy thio NAPHTHEN#, indoxyl, or derivs. in 
alk. alcohol soln., excluding air. Patent claims use of mild reducing agents to form from the 
quinones water soluble bodies whose alkali salts will condense with oxy thio naphthene. A color- 
less or almost colorless powd., insol. aq., diff. sol. alk., sol. dil. alk. (RV) which soln. is decomp. 
by acids; BLUE vat (RV) dye. 

Near S. 907—‘‘Ciba Scarlet G.”? Note 891,690 for unreduced dye of similar constitution. 
968,697—Aug. 30, 1910. 

Albrecht Scumipt, Ernst Bryk and Robert Voss, Germany. (Héchst.) 
Vat dye and process of making same. Halogen indoxyl thio indigo, thio indirubin, 
or other. 

4-Acet amino thio saLicyL acetic acid or 6-amino oxy thio naphthene and 1saTIN, or brom 
nitro amino isatin, heated in nitrobenzene soln. to 160° with bromine. Other amino-oxy thio 
naphthenes and other derived isatins are claimed. Products are dark powds., insol. agq., alc., 
C,H,, ether, dil. acids and alks., sol. in conc. H,SO, (BrV-B), diff. sol. in hot C.H,NO,, C,H.NH,, 
etc; yellow BROWN, BROWN or GRay vat (YB) dyes. 

S. 902—‘‘Helindon Brown 2 R.’”? Schulz bases three dyes, 902, 903 and 904 on this patent. 


980,140—Dec. 27, 1910. Wilhelm BaveEr and Alfred Herre, Germany. (Bayer.) 
Blue wat dye. a-Anthrol dichlor indole. 


Dichlor 1sat1n converted to chloride by PCI, in dry chlor benzene soln., then combined with 
a-ANTHROL, also in dry chlor benzene. A blue cryst. powd., sol. hot C,H, (B), in conc. H,SO, 
(olive); a BLUE vat (O) dye. 

S. 893—‘“‘Alizarin Indigo G.” Addition to 961,396. 


984,442—Feb. 14, 1911. Arnold Rantyen, Germany. 
Process for preparing indoxyls and indigo by electrolysis. Indoxyls and indigo 
by electrolysis. 


Phenyl GLycin, phenyl hydantoin, homologs, salts, ethers, acetyl derivs., etc., electrolyzed 


at 220-260° in caustic alkali soln., with or without diaphragm or flux and in vacuo if preferred, . 


with cell as cathode and carbon as anode, using current of 4-6 volts and 2-5 amps. per sq. 
dem. During electrolysis ammonia or hydrazin vapor is passed through the mass to form metallic 
amids or imids from metal set free. Reaction should be rapid at first to remove free aq. Yield 
70 per cent and upward. 

S. 874—‘“Indigo.” 


985,767—Mar. 7, 1911. 
Wilhelm Baver, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 
Vat dye. Halogen naphthindol hydroxy a-b-anthraquinonyl compound. 

Brom b-NAPHTHISATIN heated with PCl, in dry chlorbenzene to form chloride then added 
while hot to @ANTHROL in same solvent. General claims same as with 961,396 et seq. Dark blue 
cryst. powds., sol. hot C,H,NO, (B); Gray to BLACK vat dyes, fast to Cl. 

Note 958,464 and 985,768,-69,-70. 


985,768—Mar. 7, 1911. 
Wilhelm Bauer, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 
Vat dye. Dihalogen naphthindol hydroxy a-b-anthraquinonyl compound. 


Dibrom b-NAPHTHISATIN converted to chloride by PCI, in dry chlorbenzene soln. then added 
to a-ANTHROL in same solvent. Same general claims as 985,767. Dark blue cryst. powds., sol. 
hot C,H,NO, (B), in conc. H,SO, (BBk); blue Gray to BLAcK vat dyes, fast to Cl. 


Note 958,464 and 985,767. 


GROUP VII.—INDIGO AND INDIGOID 219 


985,770—Mar. 7, 1911. 
Wilhelm Bauer, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 


Vat dyestuff. Dihalogen naphthindole 4-halogen 1-naphthol. 


Dibrom b-NAPHTHISATIN converted to chloride by PCl, in hot dry chlorbenzene then added 
hot to 4-brom 1-NAPHTHOL in same solvent. General claims similar to 985,767 and products with 
similar properties. Gray-BLUE to BLACK vat dyes, fast to Cl. 


985,769—May 7, 1911. 
Wilhelm Baver, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 


Vat dyestuff. Halogen naphthindole 4-halogen or ethoxy 1-naphthol. 


Brom 6-NAPHTHISATIN converted to chloride by PCI, in dry chlorbenzene soln. then added 
while hot to 4-brom I-NAPHTHOL in same solvent. Same general claims as in 985,767. Dark 
cryst. powds., sol. hot C,H,NO, (B), in conc. H,SO, (BG-Br); Gray to BLAcK vat dyes, fast 
to Cl. 

Addition to 985,767. 


9$94,988—June 13, 1911. _ Gadient Ener and Jaroslav Frounicu, Switzerland. (Basle.) 
Yellow-colored derivatives of indigo and process of making same. Benzyli- 


dene substituted for two N hydrogens of indigo forming additional heterocylic ring, and 

sulfo derivs. 

Indigo, heated to 150-160° in nitrobenzene soln. containing Cu powder, with BENZOYL 
chloride. Soln. in fuming H,SO, yields sulfo dye. Instead of Cu, Co, Hg, or Ni salts such as 
ZnCl,, AICl,, may be used as condensing or contact substance. As solvent nitrobenzene may 
be omitted or replaced by naphthalene, xylene, etc., and for benzoyl chloride the trichloride or 
other haloid of an aromatic acid. Green to brown yellow powds., insol. aq., diff. sol. in alc., 
ligroin, easily sol. hot C,H,NO, (Y), in conc. H,SO, and oleum (Br), on diln. (Y); YELLOW 
acid dyes. 

S. 889—“Indigo Yellow 3G Ciba.” Note 997,766 and 1,026,574. 


$97,260—July 11, 1911. Wilhelm Baver and Alfred Herre, Germany. (Bayer.) 
Vat dye. a-b-Anthraquinonyl thio indoxyl compound and derivs. 
Dimethyl 4’-amino a-anilino thio 1Inpoxyr, from nitroso dimethyl ANILIN and thio INDOXYL 


in glac. acetic soln. heated in water bath with a-anruHrot. Halogen derivs. and other aryl amins 
claimed. Violet powds., sol. hot C,H, (VR-R fluor), in conc. H,SO, (G); viotet vat dyes. 


$897 ,766—July 11, rort. Gadient Ener and Jaroslav Frouuiicu, Switzerland. (Basle.) 
Halogenized vat dyestuffs and process of making same. Halogenated Indigo 

Yellow 3 G Ciba, S. 889 or derivs. 

Inpico substituted in two N. hydrogens by benzylidene (see 994, 988) by action of BENZOYL 
chloride, mixed in a diluent, such as sulfuric acid or nitrobenzene, with bromine at ordinary 
temp. then heated to 170-175°. Other halides of aromatic acids are claimed. Products are 
yellow powds., containing 33 per cent Br., insol. in aq., diff. sol. in alc., more easily in 
C,H,NO, (Y), sol. in conc. H,SO, (BrR), in oleum (BR); YELLow vat (BR) dyes, fast to 
washing, light and Cl. 

S. 890—‘“‘Ciba Yellow G.” 


998,596—July 25, 1911. 
Wilhelm Bauer, Alfred Hrerre and Rudolf Mayer, Germany. (Bayer.) 
Vat dye. Oxy acenaphthene 5.7-dibrom indoxyl compounds resembling indigo. 

Dibrom 1satTIn converted into the chloride by PCI, then added to hot soln. of 4-oxy Acz- 
NAPHTHENE in dry benzene. Other derivs. of isatin may be used with any easily replaceable 
alfa-keto group. Claims similar to 961,396. 

S. 894—‘“‘Alizarin Indigo B.” 


$99,439—Aug. 1, 1911. Karl Erse, and Edward Wray, Germany. (Kalle.) 
Vat-dyeing coloring-matter. Dibrom indoxyl 1-naphthol compound resembling indigo. 


4-Methoxy I-NAPHTHOL or other oxy derivs of cylic hydrocarbons, combined with ISATIN 
a-anilid or derivs. to form an indigoid dye, which is added slowly at ordinary temp. to a conc. 
sulfuric acid bromine mixture, (or SO,Cl,). Less Br is required when components already 


15 


220 DIGEST OF PATENTS 


contain bromine or other substituents. Blue powd., insol. aq. and alc., sol. H,SO, (GB), in 
hot C,H,NO, and C,H,NH, (B); Biur vat (Y) dyes. 

S. 893—‘“Alizarin Indigo G.”’ Although patent reference in Schulz is to this dye, the 
formula there given belongs to 961,396 by Bauer and Herre. 

S. 895—Alizarin Indigo 3R is correct Schulz number. 


1,001,457—Aug. 22, ro1t. Karl ScHIRMACHER and Richard Lrorotp, Germany. (Hdchst.) 
Green to black dyestuff. 6.6’ Dialkyl dithio deriv. of indigo. 

5-Ethyl thio phenyl GLycIN 2-carbo acid, from 4-ethyl thio ANTHRANILIC acid and chlor 
ACETIC, condensed in boiling acetic anhyd. Other s5-alkyl thio derivs. of phenyl glycin carbo 
acid are included in claims. Products are green black powds., sol. conc. H,SO, or glac. acetic 
(G), sol. in ale. or C,H,NO, (dichroic BrR-G); GREEN to BLACK vat (Y) dyes. 


1,001,919—Aug. 29, 1911. 
Wilhelm Bauer, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 
Vat dye. Dibrom indoxyl acenaphthenone indigo. 

Dibrom IsaTIN or derivs., converted to chloride by PCI; in dry benzene, then condensed 
with ACENAPHTHENONE in dry benzene soln. Claims similar to 961,396. Dyes are red brown 
cryst. powds., sol. in hot C,H, (BR), in cold conc. H,SO, (G), in hot sulf. (B); violet rep 
to VIOLET vat (V) dyes. 


1,005,140—Oct. 10, 1911. 
Wilhelm Baver, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 
Wat dye. 2-b-Naphthindoxyl-4-brom-1-naphthol compound resembling indigo. 
b-NAPHTHISATIN converted to chloride by PCI; in chlor benzene, then condensed with 4q- 
brom I-NAPHTHOL in same solvent. Claims similar to 961,396 with naphthisatin instead of 
isatin derivs. Dark cryst. powds., sol. hot C,H,NO, (B); Gray to BLacK vat (Y) dyes, fast 
to Cl. 


1,005,141—Oct. 10, 1911. 
Wilhelm Bauer, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 
Vat dye. 2-a-Naphthindoxyl a-anthrol indigo. 
b-NAPHTHISATIN converted to dichloride by PCI, in chlor benzene soln. condensed with a- 
ANTHROL. Claims similar to 961,396 with naphthisatin derivs. instead of isatin. Violet cryst. 
powds., sol. hot C,H,;NO, (B), in conc. H,SO, (B); violet Gray to red BLack vat (Y) dyes, fast 
to Cl. 


1,012,363—Dec. 19, 1911. Tudwig Kars, Germany. (Badische.) 
Indigo coloring-matter and deriwatives thereof and process of making 
them. Dehydro indigo or derivs. as stable, easily sol. bisulfite compounds. 

Inpico, halogen compound or other, oxidized in dry benzene soln. by PbO, with a little 
glac. acetic acid and dehydrating agent to form dehydro INnpiIGo or its diacetate which can be 
halogenated at once, or later. Bisulfite compound is formed by adding powd. dehydro indigo 
to cone. soln. of bisulfite (40°). Other dry solvents, CHCl, or C,H;NO,; other oxidizing 
agents, MnO,, permanganates, etc. and soluble dehydrating agents, such as anhydrous acids, 
glacial acetic, benzoic or HCl may be used. Products are specially adapted to light effects, 
printing, etc.; BLUE vat dyes. 

Near S. 874—“Indigo.” 


1,015,495—Jan. 23, 1912. Joseph Kortscuret and Andre Barrer, France. (Soc. Chim.) 
Process of producing indigo-o-nitrophenyl-lactic acid ketones. Indigo 2- 

nitro phenyl lactic acid ketones. 

2-Nitro PHENYL nitro methane, homologs or derivs, in aq. acetone soln. containing NaOH 
cooled, powd. KMnO, added slowly, filtered to remove MnO, and ketone in soln. converted 
to indigo with alkali. 

S. 874—“‘Indigo.”’ 


1,025,138—May 7, 1912. Erwin Horra, Germany. (Hochst.) 
Violet-blue dyestuffs. 4.4’-Dimethyl 5.5’-dihalogen 7.7’-dialkoxy thio indigo. 

6-Methoxy 4-chlor 3-methyl thio ciyconic acid, 1 part, condensed in 5 parts chlor sulfonic 
acid, by stirring at ordinary temp., poured on ice, filt. and purified by boiling NaOH. Other 


GROUP VII.—INDIGO AND INDIGOID 221 


halogen and alkyl derivs. claimed. Violet blue powds., insol. aq., almost insol. alc., sol. 
C,H,NO, (V), in conc. H,SO, (G); violet sug vat (V) dyes. 

S. 920—“Helindon Violet BB.” Note the isomeric dye with chlorine in 6.6’ positions is 
of a violet red color. 


1,025,174—May 7, 1912. Robert WeELDE and Benno Homoika, Germany. (Hochst.) 
Blue vat dyestuff and process of making same. Indoxyl oxy anthranol indigo. 


IsaTin a-anilid, or other alfa substituted isatin, treated in benzene soln. with PCI; to form 
chloride then condensed with a-oxy ANTHRANOL (produced by gentle reduction of a-oxy anthra- 
quinone) by heating to 100° in acetic anhyd. soln. Dyestuffs are blue cryst. powds., insol. in 
aq., slightly sol. in alc., easily sol. in xylene, phenol, C,H,NO, (B), in conc. H,SO, (V); BLuE 
vat (OY) dyes. 

S. 896—‘‘Helindon Blue 3 GN.” Note this patent claims a process previously used by Bauer 
and Herre (961,396 et seq.) and by Elbel and Wray (999,439). 


1,028,911—June 11, 1912. Albrecht Scumipt and Karl Tuirss, Germany. (Héchst.) 
Reddish-blue vat dyestuffs and process of making same.  Tribrom-7-methyl in- 
dirubin. 


IsaTin condensed with 7-methyl 1npoxyLt and halogenated in nitrobenzene soln. 2 to 5 
atoms halogen being added. Other solvents and varying amounts of bromine or chlorine are 
employed. Products are blue violet powds., insol. aq., very diff. alc., diff. sol. CHCl, (V), sol. 
in C,H,NO, and C,H,NH,, diff. sol. H,SO, (dark G); violet BLUE vat (Yt) dyes. 

S. 898—‘“‘Helindone Violet D.” 


1,042,679—Oct. 29, 1912. H. S. A. Hout, Germany. (Badische.) 


Halogenized indigo compounds and process of making such bodies. (Process 
only claimed.) Tri or tetra chlor dehydro indigo salts. 

Dehydro 1npico, a salt homolog or deriv., or the indigo itself, chlorinated in glac. acetic 
soln. in absence of comp. capable of fixing HCl but in presence of organic acid capable of 
forming salt with halogenized dehydro indigo, then reduced. Other solvents, such as nitro- 
benzene, acetyl chlorid, CCl,, etc., and other halogens or halogen derivs., such as sulfuryl chlor- 
ide in different proportions, may be used. A BLUE vat dye. 

Near S. 885—‘‘Brilliant Indigo, etc.” 


1,043,468—WNov. 5, 1912. 
Albrecht Scumipt, Heinrich R6ssNER and Hans BatHorn, Germany. (Hochst.) 
Manufacture of brominated blue indigo dyestuffs. (Product also claimed.) Bro- 
minated indigo containing at least 4 atoms Br. 

Dibrom 1npico or dichlor indigo of 856,776, converted into green black perbromid as in 
918,920, filtered from sulfuric acid, pressed and added to a conc. bisulfite soln. diluted with 
ice. Pptd. dye contains 55-58 per cent bromine (4 atoms at least), sol. conc. HOO GB); 
oxidized in glac. acetic by HNO, yields 5.7-dibrom isatin, m.p. 249-250°; BLUE vat dyes of 
green hue by artificial light. Leuco products are gray green, insol. in aq., sol. in dil. caustic 
(YBr). 

S. 881 to 887. Note 856,776 for tetrabrom indigo. 


1,043,682—Nov. 5, 1912. Gadient Ene, Switzeriand. (Basle.) 

Colored condensation products and process of making same. Diphenyl diacetoyl 
indigo condensate with two additional closed six membered rings joining CO of one indoxyl 
with N of the other. ; 

Inp1co and 2 mols. PHENYL acetic acid chloride, refluxed till HCl ceases to evolve, diluted 
with nitrobenzene or xylene and again boiled to close rings. Halogen or alkyl substituted in- 
digoes up to six or more substituents, and any other halide of an arylated fatty acid may be 
employed. Dyes may be sulfonated. Red to violet powds., insol. in aq., sol. hot xylene or 
C,H,NO, (BR-Y fluor), sol. conc. H,SO, (YO-O), pptd. on diln. (R-V); vaRI-coLoRED vat or 
acid dyes. : 


1,050,179—Jan. 14, 10913. August Stock, Germany. (Hochst.) 


Violet tetrachlorindigo and process of making same. _5.5’.6.6’-Tetra chlor indigo. 


4.s-Dichlor 2-nitro BENZALDEHYDE obtained by nitrating 4.5-dichlor BENZALDEHYDE, mixed 
in acetone soln. at 5° with aq. sod. sulfite to form dichlor phenyl lacto methyl ketone, then 


222 DIGEST OF PATENTS . 


calcined Na,CO, added and heated to 30-40°, Violet powd., insol. aq., very slightly sol. ace- 
tone and CHCl, (V), in glac. acetic (B), in cold conc. H,SO, (dull YGy) turning (G) when 
heated; a red vioLeT vat (Y) dye. 

Isomer of S. 885—‘‘Brill. Indigo.” 


1,051,856—Feb. 4, 1913. 
Wilhelm Baver, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 
Vat dye. = 5.7-Dibrom indoxyl 3-carbazole compound, homologs and derivs. 


5.7-Dibrom IsaTIN converted to chloride by PCI; in dry benzene suspension and added to 
hot soln. of CARBAZOLE in same solvent. Other isatin derivs. in which the oxygen of the alfa 
keto group is replaced by easily replaceable substituents (halogen, S, NH,, alkoxy) and other 
carbazol comps. may be used. Dyes are cryst. powds. with metallic luster, sol. hot. C,H,;Cl 
(V); RED to VIOLET vat (Y) dyes, fast to chiorine. 

Addition to 985,767. 


1,061,781—May 13, 1913. Albrecht Scumipt and Karl Turgess, Germany. (Hoichst.) 
Greenish-blue hexabromindigo. Hexabrom indigo. 


Inp1G0, or halogenated derivs., heated with excess Br to 100—120° under pressure, excess 
Br removed by distn., air, etc. and perbromide pptd. by bisulfite as hexabrom indigo. Halo- 
genation can also take place in fuming sulfuric (2-5 per cent anhyd) or in chlor sulfonic. 
Product is insol. aq., sol. conc. H,SO, (B), in cold C,H,NH, (GB-dark B), oxidized in glac. 
acetic by HNO, gives 4.5.7-tribrom isatin, m.p. 257°; a green-BLUE vat dye. 

S. 883-—‘Indigo M.L.B./6B.”” Note 1,070,541. 


1,070,541—Aug. 19, 1913. Albrecht Scumipt and Karl Tuiess, Germany. (H6chst.) 
Pentabromindigo. 4.5.7.5'’.7’-Penta brom indigo 59.8 per cent Br (theory 60.88 per cent). 

Inp1co or brom derivs., dissolved in 10 parts liquid. bromin while cooling, then gently heated 
to 80° under pressure, excess Br removed and resulting penta brom indigo heated with soln. 
of bisulfite, etc. Sulfuric acid soln. of Br may be used and preferably halogen carrier such 
as iodine. Dark blue powd. sol. in conc. H,SO, and cold C,H,NH, (B), much more sol. in 
organic solvents than tri and tetra derivs., on oxidization gives 4.5.7-tri- and 5.7-dibrom isatin; 
a BLUE vat dye with green tint perceptible by artificial light. 

S. 882—“Indigo, M.L.B. 5B.” Note 1,061,781. 


1,074,405—Sept. 30, 1913. 
Wilhelm Bauer, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 


Vat dye. 5.7.6’-Trichlor indirubin or other. 


5.7-Dichlor 1saATIN or deriv. in hot glac. acetic acid to which 6-chlor 1npoxyL or derivs. in 
same solvent then conc. HCl are added and whole heated. Red brown crysts., sol. hot C,H,NO, 
(R), in conc. H,SO, (BrR-RV); rep vat dyes, fast to Cl and light. 

Near S. 897—‘‘Ciba Heliotrope B.” ; 


1,074,850—Oct. 7, 10913. Gadient Enc1, Switzerland. (Basle.) 
Vat dyestuffs of the indigo series and process of making same. Halogenated 

leuco form of S. 890. 

Inp1co condensed with sBenzoyut chloride, halogenated, then boiled with NaHS, or other 
inorganic solvent that is water miscible (alcohol, etc.) in absence of caustic alks. Orange to 
orange brown powds., insol. aq., diff. sol. hot alc., more easily in hot C,H,NO, (BrY), in conc. 
H,SO, (RBr), pptd. on diln.; orange YELLOW vat (R) dyes, fast to washing, light and chlorine. 

Near S. 890—‘‘Ciba Yellow G.’? Note 994,088 and 997,766 (S. 890) for first part of process. 
Treatment with NaHS claimed above. 


1,081,898—Dec. 16, 1913. Gadient Enc1 and Jaroslav Froéuuicn, Switzerland. (Basle.) 
Orange vat dyestuffs and process of making same. Amino thio indoxyl acenaph- 
thene quinone. 

ACENAPHTHENE quinone or other, condensed with 6-amino thio INDOxyL or its carbo acid, 
product added at O° to a mixture of 97 per cent sulfuric and Br then heated to 20-25°. Heat- 
ing in nitrobenzene soln. or other with Br to 200-220° gives halogenated product. Brown to 
brown yellow powds., insol. aq., sol. in conc. H,SO, (B); ORANGE to brown ORANGE vat (VBr) 
dyes. 

S. 911—‘“‘Ciba Orange G.” 


p 
¢ 
1 
& 
a 
‘ 
% 
2 


GROUP VII.—INDIGO AND INDIGOID 223 


1,101,778—June 30, 1914. 
Wilhelm Bauer, Alfred Herre and Rudolf Mayer, Germany. (Bayer.) 
Vat dyestuffs, o9-Chlor naphthindoxyl a-anthrol indigo. 
g-Chlor NAPHTHISATIN or other halogen deriv. of same, converted to chloride by PCI, in 
chlor benzene, then condensed with a-ANTHROL in same solvent. Dark powds., sol. conc. H,SO, 
(B-G), sol. hot C,H;NO, (GB); rEp to BLUE to GREEN fast vat (RBr) dyes. 
Addition to 961,396. 


1,108,056—Aug. 18, 1914. - Edward Wray, Germany. (Kalle.) 
Manufacture of vat dyestuffs. (Product also claimed.) 5-Chlor indoxyl 2’.1’-pheno 

s’-oxy 6’-naphthcarbazole, homologs and derivs. 

5-Chlor 1satin 4/-chlor a-anilid, or other reactive isatin a-deriv., condensed in acetic an- 
hyd. soln. with 2.1-pheno 5-oxy NAPHTHCARBAZOLE (from PHENYL hydrazin and 2.5-amino sulfo 
NAPHTHALENE fused with alkali) or other o-phenoxy carbazoles. Dyes are powds., insol. in usual 
solvents, sol. in conc. H,SO, (GB); BLuE to vioLET vat (Y) dyes. 

Note 1,108,057. 


1,108,057—Aug. 18, 1914. Edward Wray, Gerimany. (Kalle.) 
Manufacture of vat dyestuffs. (Product also claimed.) Thio indoxyl 2.1-phen 5-oxy 

naphthcarbazole indigo. 

2.1-Pheno 5-oxy NAPHTHCARBAZOLE or other phenoxy naphthcarbazole, dissolved in glac. acetic 
containing sodium acetate to which is added thio 1npoxyL dibromide, or other alfa derivs of thio 
indoxyl in small portions. Products may be halogenated. ‘They are red violet powds., insol. 
aq., slightly sol. alc., sol. hot C,H,NO, and quinolin, in conc. sulf. (G); red violet fast vat (Y) 
dyes. 

Addition to 1,108,056. 


1,122,790—Dec. 29, 1914. Edward Mtncn, Germany. (Barlische.) 
Vat coloring-matters and process of producing them. Indoxyl perimidin (or 
thio perimidin) indigo. 

Isatin chloride or other isatin a-halogenid (from 1sat1n and PCI.) in benzene soln. added 
to boiling benzene soln. of PERIMIDIN (peri-napthimidazole) thio urea of same, or other. See 
table of components and properties. Blue tinted powds., sol. conc. sulf. (BG), sol. C,H,NO, 
(BG-VB); blue crEEN to violet BLUE vat (Y) dyes. 


1,144,577—June 29, 1915. Edward Wray and Fritz Hrss, Germany. (Kalle.) 
Manufacture of vat dyestuffs. (Products claimed.) 2-Indoxyl-6-benzoyl amino-1-naph- 

thol indigo. 

6-Benzoyl AMINO I-NAPHTHOL 5.5’-dioxy 2.2/-dinaphthyl urea or other acidyl amino naph- 
thols, and 1saT1IN a-anilid, or other alfa isatin deriv. boiled together in acetic anhyd. Dark blue 
to black powds.; BLUE to violet BLACK vat (Y) dyes. 

Note 1,147,778 and 1,157,485 for related dyes. 


1,147,778—July 27, 1915. Wilhelm Bauer and Alfred Herre, Germany. (Synthetic.) 
Red vat dye. Dichlor indoxyl phenyl a-indanon indigo. 

5.6-Dichlor 1sat1n a-anilid, or other halogen deriv. of isatin in which the alfa keto oxygen 
is replaced by a mobile substituent, heated in acetic anhyd. with 3-phenyl INDANONE, or other 
aryl indanon. Reddish powds., sol. conc. H,SO, (B); RED to vioLet fast vat (Y) dyes. 

Note 1,144,577 and 1,157,485 for related dyes. 


1,157,.485—Oct 19, 1915. : Edward Wray, Germany. (Kalle.) 
Manufacture of black dyestuffs. (Product claimed.) Chlor indoxyl oxy naphtho-car- 

bazole indigo. 

5-Chlor 1satin 4’-chlor a-anilid, boiled in acetic anhyd with 5-oxy 2.1-NAPHTHCARBAZOLE. 
Other mono chlor isatin alfa derivs. are claimed. Black powds., insol. in aq. and alc., sol. hot 
C,H,NO, and quinolin (B), in cold sulf. (slate B); fast BLackK vat (Y) dyes. 

Note 1,108,056, 1,108,057, 1,144,577 and 1,147,778. 


1,211,413—Jan. 9, 1917. Lee E. H. Const, Michigan. (Dow.) 
Method of making indoxyl and derivatives. Indoxyl or leuco indigo, and derivs., 
with improved yields. 


224 DIGEST OF PATENTS 


Phenyl ciycin, phenyl glycocol, etc., fused with caustic alkali, alk. earth oxide, and metallic 
sodium, present as such, and melt passed into water out of contact with air. The proportions 
of the ingredients in the melt are important. Yields are 65-75 per cent. 

S. 874—“‘Indigo.”’ 


1,211,413—Jan. 9, 1917. Lee E. H. Cont, Michigan. (Dow.) 
Re. 14,364—Sept. 25, 1917. Method of making indoxyl and derivatives. 


Phenyl ciycin, phenyl glycocol or similar body, added to hot melt consisting of NaOH and 
KOH in molecular proportions, also of quicklime, or other alk. earth oxide and metallic Na. 
The latter must be present as such in the fused mass. Melt is: maintained at 250° for half 
hour, then poured into water out of contact with air. 

S. 874—“‘Indigo.” Note 617,652, 727,270, and 756,171. 


1,243,170—Oct. 16, 1917. ‘Richard Herz, Germany. 
Vat dyes and process of making same. Thio indigo and derivs. 

AniL1In HCl, or other aromatic amin, dried, ground, and heated with SO,Cl, to 50-70° until 
it will not diazotize, ppt. dried in vacuum, heated in alc. NaOH containing sod. hydrosulfite 
until aq. soluble, cHLOR ACETIC in alk. soln. added and heated to 70-80°; product diazotized, 
combined with Cu(CN),, nitrile saponified, ring closed by heating in Na,S soln, boiled with 
acids and oxidized. Dark colored powds., insol. aq., dil. alks. and acids, sparingly sol. in alc., 
hot C,H, and other organic solvents, diff. sol. C,H;,NO, (R-V—Br); ORANGE, RED, VIOLET, BROWN 
and BLACK vat (Yt) dyes, fast to washing, scouring, bowking and Cl. 

Note 1,243,171 for more specific claims. 


1,243,171—Oct. 16, 1917. Richard Herz, Germany. 
Vat dyes and process of making same. Thio indigo. 

2-or 3-TOLUIDIN or 4-xylidin, subjected to same process as anilin HCl in 1,243,170. Red 
powd., sol. hot C,H,NO, (BR), in warm conc. H,SO, (dark G); a pale rep vat (Y) dye of 
great purity of shade and fastness. 


1,253,252—Jan. 15, 1918. Michael Karpos and Paul Nawrasxy, Germany, (Badische.) 
Bluish-green vat dyes and process of making them. Diaceanthrene quinone oxim 
indigoes. 


ANTHRACENE 1.9-dicarbo acid methyl imid (from METHYL amin and ANTHRACENE-1.9-di- 
carbo anhyd.) heated in KOH at 210°, melt dissolved and oxidized with air. The hydrogen of 
the imid must be substituted before alk. fusion, but dye can be alkylated or halogenated after 
it is formed. Blue GREEN fast vat (R-V) dyes. 

Note that specific claims are given above while generic claims may be found in 1,216,134. 


1,266,092—May 14, 1918. Wilhelm Baver and Alfred Herre, Germany. (Synthetic.) 
Yellowish-brown vat dyes. 6-Amino 5.7’-dichlor indirubin. 


5.7-Dichlor 1saATIN, indoxyl or acidyl derivs., and 6-nitro diacetyl Inpoxyzt heated in glac. 
acetic containing HCl. Product may be halogenated. In the vat it is converted into the amino 
comp. Nitro products are violet crysts., sol. conc. H,SO, (BV); yellow BRown vat dyes, fast 
to washing, light, Cl. The amino derivs. are dark brown powds., insol. in usual organic sol- 
vents, sol. conc. H,SO, (RV). 

Near S. 897—‘“‘Ciba Heliotrope B.’’ 


1,293,680—Feb. 11, 1910. Emmanuel A. Bourcart, France. (Comp. Paris.) 
Manufacture of indoxyl, its homologues and their derivatives. Higher yields 
in indigo manufacture. 

To a molecular mixture of NaOH and KOH, in an autoclave, sodamid, or other water de- 
composing agent, is added, and pressure raised to 6-10 atmos. by means of NH, or C,H,NH, 
vapors. At 180° one part phenyl glycin or other aryl glycin is added to the fused mixture, 
keeping temp. below 190°. When NH, ceases to evolve, melt is dissolved in ice water, and 
indigo pptd. 


1,322,052—Nov. 18, 1919. Ralph S. Porrer, New Jersey. (Barrett.) 
Process of producing anthranilic acid. Anthranilic acid from phthalimid by more 
economical process. 
PHTHALIMID is converted to ANTHRANILIC acid, Na salt, by NaOCl and NaOH, the carbonate 
in soln. recovered as ppt. of bicarbonate by addition of Co, gas, filtered, and free anthranilic 


GROUP VII.—INDIGO AND INDIGOID 225 


acid pptd. from filtrate by excess SO, gas, which will not cause loss by forming soluble salts 
with product. 


t,412,038—Apr. 11, 1922. Maurice BouviEr, France. (Soc. Chim.) 
Dyestuffs of the indigo series. Dibrom 5.5’-dimethyl indigo. 


5.5’-Dimethyl 1np1co, derived from a) 2-nitro 5-methyl BENZALDEHYDE by condensing with 
ACETONE in an alk. medium, or b) by alk. melting of 4-tolyl glycin, is halogenated by direct 
treatment with halogen in hot C,H, soln., in conc. H,SO,, or in cold SO,Cl, A dark blue 
powd., sol. in conc. H,SO,, cold C,H,NH, and alc. (G), sol. in hot C,H.NH,, in C,H,NO,,CHCI,, 
acetone, C,H,, CCl,, CS, and acetic acid (B); a sLuE vat (GY) dye, which unlike unhalogenated 
dimethyl indigo, gives deep, sharp shades. 


1,414,335—May 2, 1922. Maurice Bouvirer, France. (Soc. Chim.) 
Process for obtaining halogen derivatives of indigo and of its homologues. 
Improved chlor sulfonic acid process for halogenating indigo. 
5.5’-Dibrom indigo, its homolog or deriv., is mixed at -10° with 8 parts chlor sulfonic 
acid, 1 part Br or alk. bromide, and about 1 part P,O, or other substance having greater affin- 
ity for water than SO,. Products are sol. in conc. H,SO, (G), in C,H;NH,, C,H,NO,, CHCL, 
CCl,, acetone C,H, and alc., (B—G); violet to green BLUE vat (GY) dyes. 


1,419,720—June 13, 1922. Lee E. H. Cong, Syracuse, New York. (Dow.) 
Method of making phenylglycine bodies. Improved process for making phenylglycin 
bodies. 


A salt of chlor acetic acid is dissolved in cold aq. soln. of anizin and gradually added to 
a hot aq. satd. soln. of anilin with undissolved anilin present in sufficient amount for the re- 
action. Excess anilin is distilled off, soln. cooled, the cryst. phenyl glycin filtered and washed 
with cold aq. anilin. 


1,427,863—Sept. 5, 1922. Carl SrEpHEen, Germany. 

Process for the preparation of compounds of isatin-a-arylides with sulphur 
dioxide. Separation of isatin-a-arylids economically from sulfuric acid used in conden- 
sation. 

Reaction mixture containing the thio amid in 4 parts sulfuric acid is run into soln. of 5 
parts ammonium sulfite in 20 parts water, keeping temp. low. The sulfite comp. of isatin a- 
anilid is pptd. nearly quantitatively, and SO, set free. Less ammonium sulfite may be used 
and filtrate neut. with gaseous NH, to recover (NH,),SO,. Excess SO, may be used in amounts 
corresponding to the arylid. Vigorous stirring is recommended or acid mixture can be sprayed 
into the basic sulfite soln. whereby strong decomp. results. 


1,431,606—Oct. 10, 1922. 
Charles J. StRosAcKER and Howard J. Rupricut, Michigan. (Dow.) 
Method of making brominated indigoes. Mono to hexa-brom indigoes by improved 
process. 

Liquid bromine in quantity from 15-25 per cent in excess of theory to form desired prod- 
uct is added, at atmospheric temp. and pressure, all at once to finely divided dry indigo in ab- 
sence of any diluent, two ingredients ground together, gradually heated and kept s50-60° for 
6-7 hours, then at 90° for 7-9 hours. Charge is neut. with NaOH then sod. bisulfite added, 
grinding being continued meanwhile. Suggested form of apparatus is described with drawing 
shown. 


1,4384,983—Nov. 7, 1922. Wilhelm BaveEr and Alfred Herre, Germany. (Bayer.) 
Vat dyestuffs.  1.2-Naphth oxy thiophene 5.7-dichlor isatin, etc. 


Equimols 5.7-dichlor 1saTin and 1.2-naphth oxy THIOPHENE are dissolved in hot glac. acetic, 
mixed, and with conc. HCl are heated at 100° for 1 hour. Red brown crysts., sol. hot C,H,NO, 
(RBr), diff. sol. conc. H,SO, (RV) and in monohydrate (BV); Brown reducing vat (Y) dyes, 
fast to Cl, washing and light. 


1,442,743—Jan. 16, 1923. Charles J. SrrosackER, Michigan. (Dow.) 
Process of making phenyl glycine. 
Three parts ANILIN and 1 part chlor acetic acid with 25 per cent aq. are slowly heated 


226 DIGEST OF PATENTS 


until reaction starts then reaction allowed to reach completion without further heating. Reac- 
tion takes about 45 mins. Brive reducing vat dye. 
S. 874—“Indigo.”’ 


1,444,277—Feb. 6, 1923. Maximilian P. Scumipt and Heinrich Rorss, Germany. (Kalle.) 
Manufacture of dyestuffs. (Product, not process, claimed.) Thio indigo derivatives. 


NAPHTHALENE 2.6-disulfo chloride in about 4 parts diluted alcohol (4:1) is reduced with 
2 parts Zn dust to disulfinic acid, then by further reduction with HCl to insol. disulfid, again 
reduced by alk. hydrosulfite to NAPHTHALENE 2.6-dimercaptan, condensed in same soln. with 
equimol. chlor acetic acid and naphthalene 2.6-dithio cLycotic acid pptd. by HCl. The latter 
may be oxidized or dissolved in 10 parts chlor sulfonic acid or other reactive CO or CS comp. 
at O° with YBr color to form naphthalene 1.2.5.6-bis (oxy thiophene), which on standing 
is transformed into thio indigo. Other naphthalene dithio glycolic acids,’ brom and chlor de- 
rivs., etc., are claimed. GrrEn, dull vioLET to BRowNn reducing vat (VR-BrY) dyes. 


1,461,435—July 10, 1923 


Hermann SraupIncER, Germany; Hans Veracuts and Richard TosierR, Switzerland. (Basle.) 
Indigoidie dyestuffs and process of making same. 


2-Thio NAPHTHISATIN, m.p. 153°, derived from oxatyt chloride and thio 2-NAPHTHOL, and 
equimol. oxy thio NAPHTHENE or other cylic comp. with reactive methylene group, such as ind- 
oxyl, thio indoxyl, pyrazolone, acenaphthenone, 1-oxy anthracene, 1-naphthol, or derivs., are 
added with cooling to about 6 parts H,SO,, then an equal amount glac. acetic further added. 
Dark powds., sol. in 98 per cent H,SO, (BrV-BG); fast RED to BRown reducing vat dyes. 


1,466,687—Sept. 4, 1923. Wilhelm Bauer, Germany. (Bayer.) 
Indigoid wat dye. 5’7'-Dichlor isatin a-6-methoxy 1-naphthol. 

5.7-Dichlor 1saTIN in dry benzene soln. is converted to alfa chlor deriv. by PCI, and con- 
densed with equimol. 6-methoxy 1I-NAPHTHOL, also in benzene soln. Dibrom isatin is also claimed 


and the black dye obtained by treating product with SO,Cl, at 70° in chlor benzene soln. Dark 
blue coppery powds.; gray-BLUE, oOlive-GREEN or green-GRAY to BLACK reducing vat (Y) dyes. 


1,467,598—Sept. 11, 1923. Max Wyter, England. (British Dyes.) 
Manufacture of phenyl glycine compounds. Producing phenyl glycin with less 
anilin. 


One mol. trichlor ETHYLENE is gradually pump d into 1 mol. (plus 5 per cent) ANILIN and 
excess milk of lime, keeping temp. in pressure vessel at 170-180°. Excess anilin is always 
present as it first enters into combination to form ethylene triphenyl triamin then is hydrolyzed 
in same mixture to phenyl glycin, thus releasing anilin for further reaction. 


1,473,887—Nov. 13, 1923. 
Charles J. StrosacKER and Howard J. Rupricut, Michigan. (Dow.) 
Method of making brominated indizgos. 

Dry INDIGO is brominated at 7o-80° under atmospheric pressure by allowing varying 
amounts of bromine to react directly with or without presence of an inert diluent such as CCl,. 
From 1-8 bromine atoms can be introduced by employing an excess of Br varying from 15 to 
60 per cent and by varying the time of reaction up to 10-12 hours. Buiuer reducing vat dyes. 


Group VIII.—INDOPHENOL. 


261,518—July 18, 1882. Horace Korcuiin and Otto N. Wirt, Germany., 
Manufacture of blue and violet coloring-matters. (Product also claimed.) Indo- 
phenols. 


Nitroso dimethyl anit1n HCl, reduced in aq. soln. at 50° with Zn to 4-amino dimethyl 
ANILIN and to this is added a mixture of pHENoL, NaOH and K.Cr,0,, then excess acetic acid. 
BLvE to vioLet direct or developed dyes that can be developed on fiber as dye or printing comp. 
Patent claims action of nitrosamins or phenols, chlorquinonimid, etc., upon a phenol in pres- 
ence of a reducing agent or of a para amino comp. in presence of oxidizing agent. Brug hydro- 
sulfite vat dyes. 

S. 619—‘‘Indophenol.”’ 


> es 


ee a a ae 


! 
; 


GROUP IX.—NITRO DYES 227 


263,341—Aug. 29, 1882. Horace Korcuuin and Otto N. Witt, Germany. 


Manufacture of blue coloring-matters called ‘“Indophenols.’”’ (Product also 
claimed.) Indophenols by improved method, sol. in aq. 


Mixture of nitroso dimethyl aniuin, free base, of 1-naphthol and alcohol heated at 100°, 
NaOH added and alcohol distilled off. No reducing or oxidizing agent employed, simply heat, 
for condensation. Brug reducing vat dyes. 

S. 619—‘‘Indophenol’’-naphthol derivs. 


275,774—Apr. 10, 1883. Horace KorcHiin and Otto N. Wirt, Germany. 
Treatment of indophenols. lLeuco indophenols. 


INDOPHENOL as fine paste is made strongly alkaline, heated gently, and grape sugar or other 
reducing agent added till liquid is yellow green. Leuco dye bath may be used at once or leuco 
dye pptd. by acid. Acid reducing agents also claimed. Dye must be oxidized on fiber and is 
suitable for printing. 

Note 261,518 and 263,341. 


617,628—Jan. 10, 1899. 
Heinrich A. BErRntHSEN, Ger. and George F. JauseErt, France. (Badische.) 
Blue dye and process of making same. 


Oxy naphth InpopHENoL thio sulfo, derived by oxidation of equimols. of para diamin thio 
sulfo acid and 1-AMINO 2-NAPHTHOL 6-sulfo acid, is dissolved in 5-10 parts conc. H,SO, and 
heated at 1oo° till soln. is green and is pptd. on diln. Buus direct or acid mordant (Cr) dye, 
fast to light and washing. 

Note Ser. 662,179. (12/27/97). 


Group IX.—NITRO DYES. 


[bee note with Explosives, Group XXIV (e).] 
225,108—Mar. 2, 1880. Heinrich Caro, Germany. (Badische.) 
Coloring-matter obtained from alpha-naphthol.  2.4’-Dinitro-1-naphthol 7-sulfo. 


I-NAPHTHOL, sulfonated, then nitrated. Methods for using conc. and fuming sulfuric given 
and tests for end of reaction and purification. The free sulfo acid is easily sol. in aq. and 
alc., insol. in hydrocarbons, CHCl,, CS,, ether and conc. mineral acids, soln. is yellow and 
strongly acid, its salts with alks., alk. earths, Al., and Zn are sol. in aq., the K., Ba and Pb 
salts only sparingly in hot aq.; it is a yELLow acid dye that will not rub off, suitable for print- 
ing and for mixtures with other acid dyes. 

S. 7—“‘Naphthol Yellow S.” 


244,757—July 26, 1881. Emil LasyHarpt, Germany. (Hochst.) 
Coloring-matter from tetranitro-naphthol. Tetra nitro naphthol. 


Brom NAPHTHALENE, 3 parts, added to 12 parts fuming HNO,, dild., dinitro derivs. sep- 
arated, washed, then heated with 8 parts sulfuric (1.84) containing fuming HNO,, to obtain 
mixture of isomeric tetra nitro brom naphthalenes, from which the one claimed in patent is 
separated by greater soly. in acetic acid, benzene, etc., then digested in warm dil. soda soln. 
to form naphthol. Chlor deriv. of naphthalene may be used. A yELLow and orancE acid dye. 

- No S. number—‘‘Heliochrysin.” 


256,379—Apr. 11, 1882. Carl Rumprr, Germany. 
Manufacture of dye-stuff or coloring-matter. A mono, di, or tri nitro 2-naphthol 
sulfo. 


2-NAPHTHOL 1-sulfo nitrated, with 50 per cent HNO,, at 30-40°, and soln. neut. with K,CO, 
or other. Proportions of ingredients and temp. may vary. Product is yellow cryst. powd.; a 
YELLOw acid dye. 


289,543—Dec. 4, 1883. Ivan L&vinstern, England. 
Manufacture of yellow coloring-matter. Nitro oxidized nitroso-1-naphthol sulfo. 
I-NAPHTHOL disulfonated with H,SO, (170° Tw) at 130°, treated with nitrous acid below 
10°, then allowed to stand 3 days with dil. HNO, (1:1) or heated to boil (less satisfactory). 
Product forms yellow earthy lumps, easily pulverized, is odorless and has acid properties; it is 


a YELLOW acid dye. 
Probably S. 7—‘‘Naphthol Yellow S.” 


228 DIGEST OF PATENTS 


300,874—June 24, 1884. 
Fritz Krucer, Georg Tosras and Eduard Krcrr, Germany. (Beyer, Kegel.) 


Production of coloring-matter from dinitro-phenol. 2.6-Dinitro phenol sulfo. 
2-Nitro PHENOL 4-sulfo acid or phenol 4-sulfo, nitrated, using H,SO, and saltpeter or 
mixed acids, then pptd. with potash, Ammonia salt is formed by evapn. to dryness with 
excess NH,OH. It is an orange-rEp acid dye. 
Near S. 5—‘‘Picric Acid.” 


324,615—Aug. 18, 1885. Leo VicGnon, France. 
Manufacture of coloring-matter from alpha-naphthol and dinitro-naph- 
thol. Mixture of disulfo 1-naphthol and trinitro 1-naphthol. 

I-NAPHTHOL, I part, sulfonated in 6 parts 66° H,SO, near boil till liquid, cooled and dild. 
by ice and nitrated with 40° HNO, below 30°, heated to 40°, cooled to 12-15°, filt. redissolved 
and pptd. with potash. Product is a yELLOwW acid dye. 

Near S. 7—‘‘Naphthol Yellow S.” 


333,036—Dec. 22, 1885. 
Heinrich Voitiprecut and Carl Mznscuinc, New York. (Schoellkopf.) 


Nitronaphtholsulphonie acid. Nitro 1-naphthol sulfo. 

NaPHTHALENE 1-sulfo, lime salt, mixed with 2 parts H,SO, (66°) and less than 0.5 part 
HNO, (40°), heated at 90-100°, two resulting nitro sulfo acids convertel into amino derivs., 
sepd. by unequal soly. in aq., less sol. deriv. diazotized, diazo body boiled in dil. H,SO, to 
form naphthol, disulfonated by heating to 80-90° with 2-3 parts H,SO, (66°) till sol. in aq., 
and Na salt formed. Resulting 1-NAPHTHOL disulfo acid is nitrated at 60-70° with 54 per cent 
HNO, and potash salt formed. It is a yvELLOw acid dye, of redder shade than Naphthol 
Yellow S. 


Note 333,034 to 9, inc., and 144, 652. 


666,627—Jan. 22, 1901. Max NEUMANN, Germany. (Westfalisch.) 
Process of making picrie acid. sym-Trinitro phenol from anilin. 


ANILIN converted by fuming H,SO, to suLFANILIc acid, diazotized, sepd. and added to HNO,, 
so that final conc. is 40°,. gently warmed till N begins to evolve, then let stand 36 hours. 
Yield is 90 per cent. 


S. 5—‘‘Picric Acid.” 


743,778—Nov. 10, 1903. Joseph Turner, England. 
Yellow dye and process of making same. Tetra to hexanitro diphenylamin. 
2.2'-Dinitro DIPHENYLAMIN 4.4/-disulfo in 25 per cent HNO, heated to 80~-g90° till partly 
pptd. Dyestuff is a yellow powd., easily sol. hot aq., sol. conc. H,SO, (OY); a greenish YELLOW 
acid dye, fast to light, that levels and penetrates well. 
(1904) S. 6—‘‘Aurantia.” 


763,756—June 28, 10904. Benno Homo.ixka and Josef Erser, Germany. (Ho6chst.) 
Process of reacting on nitramins with formaldehyde and a product there- 
of. 5.5’-Dinitro 2.2'-dinitroluidino-methane. : 
5-Nitro 2-TOLUIDIN, m.p. 107°, or other primary aromatic nitramin, as salt, mixed with 
sufficient 40 per cent FORMALDEHYDE. Products are yellow to orange yellow powds., insol. aq., 
little sol. in org. solvents, sol. in hot glac. acetic acid; YELLOW lake dyes. 


S. 8—‘“‘Pigment Chlorine GG.” 


932,266—Aug. 24, 1908. Ernst Fuss—ENEGGER, Germany. (Badische.) 
Yellow dye and process of making. 5.5’-Dichlor 2.2’-dinitro diahilino methane. 
5-Chlor 2-NITRANILIN aS IO per cent paste, two mols., heated in closed vessel at 70-80° 
with 1 mol. FORMALDEHYDE, 30 per cent soln. Product is yellow powd. m.p. 210°, diff. sol. alc., 
easily sol. hot xylene; a greenish YELLOW lake dye, fast to lime, light, aq., and alc. 
Note 955,080. 


GROUP IX.—NITRO DYES 229 


955,080—Apr. 12, 1910. Paul Jutius and Ernst Fuss—ENEcGER, Germany. (Badische.) 

Yellow dye and process of making same. 4.4/-Dichlor 2.2’-dinitro dianilino methane. 
4-Chlor 2-NITRANILIN heated to 7o—80° in closed vessel with FORMALDEHYDE. Product is a 

yellow powd., m.p. 262°, fairly sol. hot xylene; an orange YELLOW lake dye, fast to light. 
Near S. 8—‘‘Pigment Chlorin.” Note 932,266. 


1,059,571—Apr. 22, 1913. Robert ScuMipLin, Germany. (Héchst.) 
Yellow to brown wool-dyestuffs and process of making same. 2.4-Dinitro 4’- 
anilino 3’-sulfo diphenylamin and homologs. 
4-Amino DIPHENYLAMIN 2-sulfo, Na salt, in aq. soln. mixed at 100° with 1-chlor 2.4-dinitro 
BENZENE, a little powd. chalk being present to neut. acid, and product converted to Na salt. 
Tolyl and other aryl derivs. are claimed. Products are dark colored cryst. powds., easily sol. 
hot aq., and are YELLOW to BROWN acid dyes, fast to light and alk. 


1,162,109—Nov. 30, 109015. Robert ScHMIDLIN, Germany. (Hochst.) 
Brownish-yellow wool dyestufis and process of making same. _§ 4.4'/-Diamino 
3-sulfo 2/-amino diphenylamin, in which one para amino group contains an aryl and the 
other a 2”.4”-dinitro residue, while the 2-position may or may not contain an aryl-oxy 
residue. 
4-Phenoxy 2’.4’-diamino DIPHENYL METHANE 3-sulfo with 2 or 4 position substituted by 
aryl amino or aryl oxy residue, in dil. Na,CO, soln. stirred for several hours at 100° with 1 mol. 
1-chlor 2.4-dinitro BENZENE. Products are brown to black powds., diff. sol. cold aq., easily sol. 
hot aq. and alc.; brownish YELLOW acid mordant (Cr) dyes, fast to washing, light and alk. 


1,166,80S—Jan. 4, 1916. Louis BLancry, Germany. (Badische.) 
Pigment. Nitro amino benzophenone or nitro amino sulfo benzid and derivs., in which the 
nucleus consists of two phenyl groups united by a polyatomic group of less than four atoms 
and containing oxygen. 
3.3/-Dinitro 4.4’-diamino sulfo BENZID, or 3.3/-dinitro 4.4’-diamino BENZOPHENONE, or other, 
mixed in dry or paste form with Al (OH),, dried and ground. Other components and lake bases 
claimed. Resultant lakes are YELLOW with good covering power, fast to aq., oil, lime, alc., and 
light, and suited for printing, lithographic inks, and fine pigments. 


1,299,171—Apr. 1, 1919. Arthur G. Green, England. 
Manufacture of picric acid. 2.4.6-Trinitro phenol by improved process. 

Dinitro PHENOL, (produced by chlorinating BENZENE, nitrating the chlor BENZENE with mixed 
acid, and converting the dinitro chlor BENZENE into dinitro phenol by boiling with caustic alk.), 
nitrated at 100° in mixed acid containing 1 mol. HNO,. Yield is nearly theoretical. Patent 
gives detailed advantages of new method. 


S. 5—‘Picric acid.” 


1,349,802—Aug. 17, 1920. lL. G. BapirEr and lL. B. Horiipay, England. (Holliday.) 


Process of manufacture of picric acid. 2.4.6-Trinitro phenol, from a commercial 
product. 


Dinitro PHENOL mixed with 2.5 parts or 98 per cent H,SO, then about 1 part mixed acid 
(98 per cent H,SO, and 42° HNO, 1:1) with HNO, from 3-7 per cent in excess of theory is 
added, keeping temp. at 20-30° for 12 hours. Temp. and conditions may vary. No nitrous fumes 
are evolved and temp. is a normal one. 

S. 5—‘‘Picric Acid.” 


1,380,186—May 31, 1921. Theodore J. Brewster, New Jersey. 
Process of making nitrophenolic compounds.  2.4.6-Trinitro phenol by more eco- 
nomical method, with less loss and increased yield. 

BENZENE, PHENOL, or other appropriate ring comp. is mono nitrated with a limited .quantity 
of HNO,, keeping temp. below 60° by artificial cooling; or a phenol is first sulfonated then 
nitrated at low temp., and then tri-nitrated with HNO, at 100°. 

Sy s—‘Picric Acid.” Note 1,380,185. 


230 DIGEST OF PATENTS 


1,393,714—Oct. 11, 1921. C. M. A. Stine and J. L. Gitson, Delaware. (du Pont.) 
Process of producing picric acid. 2.4.6-Trinitro phenol in reduced operating time, 
and more economically. 

Dinitro PHENOL suspended in H,SO, (1.5 parts of 92-98 per cent) at room temp., heated to 
71° and mixed acid (80 per cent HNO,) gradually added during 2 hours with temp. 71-94° until 
15 times the theoretical quantity HNO, is present, then temp. raised to 94-113° for one hour, 
cooled to 25-52°, and spent acid containing 75 per cent H,SO,, 2 parts, further added. 


1,396,001—Nov. 1, 1921. David B. Macponatp, England. 
Manufacture of picric acid. 2.4.6-Trinitro phenol, pure, of high m. p., and free from 
metallic contamination, with reduced danger to workmen. 

BENZENE is nitrated by usual methods with HNO, and Hg as catalyst or with action of alk. 
nitrate on a sulfonated PHENOL, at a low temp. of 35°, thus restraining the nitration and oxida- 
tion, excess NITROBENZENE is driven off by steam, residue recryst. from benzene, and benzene 
recovered. Apparatus is described in detail. 

S. 5—‘‘Picric Acid.”’ 


1,412,707—Apr. 11, 1922. W. B. RicHarpson, North Carolina. 
Brown dye and process of making same. Possibly a mixture containing some mono 

nitro 1.5-dioxy naphthalene. 

1.5-Dioxy NAPHTHALENE slowly added to 10 parts HNO, (1.3), stirred 1 hour, then 15 
parts HNO, (1.42) further added, stirred, let stand half hour and poured into water to ppt., 
all being carried out at room temp. A brown powd., slightly sol. aq., dil. HNO, and H,SO,, sol. 
in NH, and Na,CO, solns., decomp. by HNO,, 1.42, containing 3.75-5.5 per chat N; a BROWN 
direct axe for silk and wool and grey brown on tannin mordanted cotton. 


1,413,914—Apr. 25, 1922. lL. B. Horttipay and J,. G. Baprer, England. (Holliday.) 
Process of manufacture of picric acid from dinitrophenol in crystal form 

and the elimination therefrom of the sulphate of lead. 2.4.6-Trinitrophenol 

pure and free from lead. 

Dinitro PHENOL is dissolved in 25 parts conc. H,SO,, to which HNO,-H,SO,, (about 1:1 with 
3.7 per cent HNO, in excess of theory), is added, keeping at 20-30°, then the mass is heated 
to 85°, steam blown in to raise the temp. above the m. p. of picric acid, stirred, cooled, and 
filtered at 25-30° to separate the picric acid from the bulk of PbSO, in soln., and crysts. washed 
with dil. H,SO, of sufficient strength to dissolve PbSO, at 25°. 

SS. .s—“Picric Acid.” 


Group X.—NITROSO. 


316,036—Apr. 21, 1885. Otto HorrMann, Germany. (Cassella.) 
Coloring-matter derived from naphthol. (Process claimed.) Ferro bis=(nitroso 1- 
naphthol 4-sulfo). 

Nitroso 1-NAPHTHOL 4-sulfo, or any nitroso naphthol sulfo except 2.1 and disulfo 2.6.8, 
oxidized with FeCl. or other iron salt. Or naphtholsulfonic acids may be treated with nitrous 
acid and iron or its salts. Dye is a green powder, easily sol. in cold aq. (YG), insol. in alc., 
benzene, or glac. acetic., unaltered by alks., destroyed by strong mineral acids, iron component 
pptd. by (NH,),S; a GREEN acid dye that may be mixed with indigo carmine. 

S. 4—‘‘Naphthol Green B.” 


862,835—May 10, 1887. Thomas Hoiuipay, England. 
Process of dyeing. (Product claimed.) Metallo bis=(nitroso 1-naphthol sulfo.) 

Wool fiber mordanted with bichromate immersed in bath containing nitroso 1-NAPHTHOL (or 
beta comp.). Other chrome, iron, copper or lead salts and nitroso naphthols are claimed, and re- 
verse process—wool first in nitroso bath, then mordant bath. 

Near S. 4—‘‘Naphthol Green B.” Note 355,933, 34 and 35. 


386,247—July 17, 1888. Thos. Hotiipay, England. (Holliday.) 
Process of dyeing. (Product also claimed.) Metallo-bis-nitroso-1-naphthol-sulfo. 

Process of mfr. is practically the same as in 362,835, the color being applied in the latter 
to wool fiber and in the present patent to cotton or other vegetable fiber. 

Near S. 4—‘‘Naphthol Green B.” 


413,724—Oct. 29, 1889. Henry D. Kenpatut, Massachusetts. 


Brown dye _ (Process claimed.) 
Dinitroso RESORCIN, 3 mols., or other, treated with sodium hydrosulfite (from Zn and 


Sr ee ee ee a ee ee ee 


GROUP XI.—OXAZIN 231 


NaHSO,). A Brown acid mordant dye, fast to soap, light, air and acids, and may be mixed 
with anthracene colors. 


420,311—Jan. 28, 1890. Alcide F. Porrrier, France, 
Nitroso dye. An azin dye, see Group V. 


Group XI.—OXAZIN. 


252,273—Jan. 10, 1882. James H. Srespins, Jr., New York. 
Purple dye-stuff or coloring-matter. Dimethyl 3-amino phen naphth oxazin. 

Nitroso dimethyl anit1n HCl with Na salt of 2-NAPHTHOL sulfo to 119° then 121°. VIOLET 
acid mordant dye. (Fe or AI.) 

S. 649—‘“‘New Blue R” sulfo. Note 255,349 for similar dye developed on fiber. 


252,274—Jan. 10, 1882. James H. Sressins, Jr., New York. 
Manufacture of blue coloring-matter. (Product, not process, claimed.) Dimethyl 3- 
amino phen naphth oxazin sulfo. 


Nitroso dimethyl anrLt1n HCl reduced in aq. by Zn dust to 4-amino dimethyl anriLin, and 
filtrate with 1-NAPHTHOL sulfo condensed and oxidized in alk. bichromate soln., then pptd. by 
acetic acid. BLur to GREEN acid mordant (Cr) dyes. 

Note 255,350. 


253,4435—Feb. 7, 1882. James H. Srepsins, New York. 
Coloring-matter or dye-stuff. Dimethyl 3-amino 5-methyl phen oxazin. 


Nitroso dimethyl ANILIN reduced with Zn dust in acid soln. to dimethyl 4-rHENYLENE DIAMIN 
which with 2-cRESOL, is oxidized in alk. soln. with Ca(OC1),. BLvuE acid mordant (Cr, Al) dye. 

Note 253,444 oxidized with bichromate. 253,445 employs phenol (for cresol) and CaQOCl,; 
254,064 employs 1-naphthol sulfo and bichromate; 254,065 employs 1-naphthol. 


253,444—Feb. 7, 1882. : James H. Sreszins, Jr., New York. 
Coloring-matter or dye-stuff. Dimethyl 3-amino 5-methyl phen oxazin. 

Patent is similar to 253,443 but oxidized with bichromate instead of Ca (OC1),. BuvE acid 
mordant dye. (Cr- AI.) 

Addition to 253,443. 


253,445—Feb. 7, 1882. James H. Sressins, Jr., New York. 
Coloring-matter or dyestuff. Dimethyl 3-amino phen oxazin. 

Patent similar to 255,443 but employs phenol for cresol and oxidizes with Ca (OC1),. BLuE 
acid mordant (Cr.Al) dye. 

Addition to 253,443. 


253,721—Feb. 14, 1882. Horace Korcuiin, Germany. 
Manufacture of colors or dye-stuffs. Dimethyl gallocyanin. 

Nitroso dimethyl ANILIN or other tertiary amin heated in aq., in alc. or acetate soln. with 
GALLIC acid or other principle analogous to tannin. VuonEtT acid mordant (Cr) dye. 

S. 626—“Gallocyanin D H.”’ Note 257,498 for leuco dye formed by reduction with Zn in 
neut. or alk. soln. and 962,712 (Lommel) by reduction with Zn and HCl or electrolytically. 


254,0G4—Feb. 21, 1882. James H. Sressins,Jr., New York. 
Dye-stuff or coloring-matter. Diethyl 3-amino phen naphth oxazin sulfo. 

Similar to 253,443 but employs 1-NaPHTHOL sulfo instead of cresol, with bichromate as 
oxidizing agent. Biur direct or acid mordant (AI,Cr) dye. 


254,065—Feb. 21, 1882. James H. Stessins, Jr., New York. 
Dye-stuff or coloring-matter. Diethyl 3-amino naphthoxazin. 

Similar to 253,443 but employs 1-NAPHTHOL, and bichromate. Buuk acid mordant (Cr, Al, 
etc.) dye. 


255,350—Mar. 21, 1882. James H. Srespins, Jr., New York, 
Manufacture of blue coloring-matter. Diethyl 3-amino phen oxazin. 

Nitroso diethyl anriL1n HCl reduced in aq. at 60° with Zn dust to form diethyl 4-PHENYLENE 
DIAMIN, filtrate condensed and oxidized with PHENOL, in alk. bichromate soln., then*pptd. by 
acetic. Brive acid mordant or direct dye, fast to alk. 

Addition to 252,274. 


232 DIGEST OF PATENTS 


348,816—Sept. 7, 1886. Haydn M. Baker, New York. 
Resorcin-blue compound. (Process also claimed.) Two amidogen groups combined with 
three resorcin rests C,,H,,N,O,. 


Resorcin dissolved in dil. NH,, with equal weight of cuprammonium carbonate and copper 
plate dipped or rotated in soln. keeping alk. with NH,. The ammonia suboxide of copper formed 
dissolves in excess NH, and acts like battery. Soln. is neut. with HCl, filt. etc. or treated with 
sheet of Zn metal to ppt. Cu, then dye pptd. by acid. Buiur acid mordant dye giving dyeings like 
indigo, suitable for lakes. 


364,320—June 7, 1887. Eduard Uuuricu, Germany. (Hochst.) 
Nitrosophenyl-blue dye-stuff. Nitroso phenyl blue, or tolyl gallocyanin, etc. 
4-Nitroso phenyl ToLtyL amin from nitrosoamin by treating with alc. HCl, condensed in 
glac. acetic with GALLIC acid or other phenol or oxy carbo acid at 100°. Green-BLUE acid mordant 
(Cr, Fe) dye, suitable for printing. 
Note 366,356. 


366,356—July 12, 1887. Eduard Uuiricu, Germany. (Hochst.) 
Blue coloring-matter formed by the action of paranitroso-diphenylamines 

on phenols or oxycarbonie acids. Phenyl gallocyanin. 

4-Nitroso DIPHENYLAMIN prepared from diphenyl niTtrosamin and alc. HCl, condensed in 
20 per cent acetic soln. with GaLLic acid by heating at 100°. Buus acid mordant (Cr, Fe) dye, 
suitable for printing. 

Addition to 364,320. 


366,357—July 12, 1887. Eduard Uuiricu, Germany. (Hochst.) 
Blue ecoloring-matter formed from paranitroso-methyldiphenylamine on 
phenols or oxycarboniec acids. Phenylated gallocyanin. 
4-Nitroso methyl DIPHENYLAMIN in glac. acetic or alc. soln., heated at 100° with GaLuic acid. 


BuveE acid mordant (Cr, Fe) dye, suitable for printing. 
Near S. 626—‘‘Gallocyanin DH.” 


396,574—Jan. 22, 1880. Alfred Kern, Switzerland. 
Formation of purple coloring-matter. (Product, not process, claimed.) Alkyl ester 
of dimethyl gallocyanin. 


Nitroso dimethyl ANILIN and methyl Gauuic acid, 1 mol. each, condensed by boiling in methyl 
alcohol. Blue vioLtet acid mordant dye, suitable for printing. 
S. 636—‘‘Prune.” 


404,309—May 28, 1889. Jakob Scumip, Switzerland. (Basle.) 
Blue azo dye. Dimethyl 3-amino phen-naphth oxazin. 


I-NAPHTHYLAMIN coupled with diethyl 3-amino PHENOL, or other, in glac. acetic soln., reduced 
with HCl and Zn dust, and resulting amino compounds oxidized with bichrom. BLveE basic mor- 
dant dye. 

Probably S. 655—‘‘Nile Blue A.”’ Note 402,980 and 431,541. Patentee calls this an azo dye. 


410,733—Sept. 10, 1880. Rodolph Gerrcy, Switzerland. (Geigy.) 
Process of making a violet dye. Dimethyl 3-amino phen-naphth oxazin. 


Amid of dimethyl ANILIN nitroso DIMETHYLANILIN condensed with GALLAMID by heating in 
acetic acid soln. VuioLer acid mordant (Cr) dye, suitable for printing as bisulfite comp. 


S. 637—‘‘Gallamin Blue.” 


413,562—Oct. 22, 1880. Alfred Sarauw, Switzerland. (Durand.) 
Production of coloring-matter. Apparently a double oxazin similar to S. 649. 
Nitroso dimethyl ANILIN, 2 mols., or other tertiary aromatic amin, gently heated in alc. soln. 
with 2.7-dioxy NAPHTHALENE (m.p. 186°) until nitroso comp. disappears. Buiuer direct or acid 
mordant, dye. 
Near S. 649—‘‘New Blue,” ‘Meldola’s Blue,” or 635, ““Muscarin.” Patent claims azo dye. 
See also 252,273. 


GROUP XI.—OXAZIN 233 


420,164—Jan 28, 1890. Johannes Mouter, Switzerland (Basle.) 
Blue dye. Anilid of dimethyl gallocyanin, or other. 

Nitroso dimethyl anILIN or other, condensed with anilid or other amid of GaLuic acid or other 
tannin by boiling in dil. acetic acid or in alc. Buur to blue viotet acid mordant (Cr or Al) or 


acid dye, suitable for printing, used as a bisulfite comp. to render soluble in aq. 
S. 639—‘“‘Gallanil Violet” or B S (bisulfite comp.). 


440,359—Nov. 11, 1890. Carl A. Mayer, Switzerland. (Durand.) 
Blue dye. (Process also claimed.) Naphthylamid of dimethyl gallocyanin. 

Nitroso dimethyl ANILIN condensed with GALLO NAPHTHYLAMID derivs. from tannin GALLIC 
acid, or other and 1- or 2-NAPHTHYLAMIN or other. Violet RED to blue vioLEtT acid mordant and 
acid dyes, reduced with alk. bisulfite for dyeing purposes. 

S. 639—‘‘Gallanil Violet.”” Note 253,721 for original gallocyanin patent. 


440,536—WNov. 11, 1890. Rene Bown, Germany. (Badische.) 
Blue dye. Dimethyl-3-amino-6-oxy phen oxazin carbo-8-carbo acid. 
3.5-Dioxy BENzoIc acid made by melting 3.5-disulfo BENzoIc in KOH, is heated in much water 


to 70° and 2 mol. nitroso dimethyl anin1n HCl slowly added. Buus direct or acid mordant (Cr) 
dyes that dye well in mixtures with such colors as alizarin. 


431,541—July 1, 1890. ' Theodor Reissic, Germany. (Badische.) 
Blue dye. as-Diethyl-3.6-diamino phen. naphth-oxazin. 

I-NAPHTHYLAMIN HCl condensed in glac. acetic soln. with nitroso diethyl 3-amino PHENOL. 
BuvE basic mordant dye. 

S. 658—‘‘Nile Blue A.”’ Apparently same dye as 404,509 (Schmid). 


442,680—Dec. 16, 1890. Meinhard Horrmann and Arthur WeinBrrc, Germany. (Cassella.) 
Blue dye. Tetramethyl 3.6-diamino naphth phenoxazin. 


Dimethyl 3-amino naphth PHENOxAzIN HCl (‘‘Meldola’s New Blue R’’) powd., mixed with aq. 
40 per cent soln. of DIMETHYL amin, product oxidized by air at 15°, and pptd. as HCl salt. 
Bichromate, FeCl, or peroxide in acid soln. may be used for oxidation. Green BLUE basic mor- 
dant dye. 

S. 651—‘‘New Methylene Blue GG.” Inventor claims addition of basic N(CH,), group and 
loss of H, probably with formation of new chromophore. 


444,538—Jan. 13, 1891. Johannes Monier and Carl A. Mayer, Switzerland. (Durand.) 
Blue dye. (Process also claimed.) Sulfo derivs. of alphyl gallocyanin anilid. 


Dye obtained in 420,164, from nitroso dimethyl ANILIN, ANILIN, and TANNIN, heated with 10 
parts ANILIN on oil bath at 158°, and product heatéd in 4 parts conc. H,SO, at 100° or fuming 
acid, (20 per cent SO,) at 15-18°. Buiue acid and acid mordant (Fe, Cr) dyes. 

Near S. 646—‘‘Corein AR.” Note 420,164 and 440,359. 


451,502—May 5, 1801. Johannes Mouter and Carl A. Mayer, Switzerland. (Durand.) 
Blue dye. Gallocyanin anilid. 


Nitroso dimethyl aniz1n HCl acted upon by condensation product of TANNIN with ANILIN and 
product heated in 4 parts 90-95° H,SO, containing no anhyd., at 80°,— see test for end of re- 
action. Buus acid dye. 

S. 639—‘‘Gallanil Violet R.” Note 420,164, 444,533 and 440,359. 


454,535—June 23, 1891. Albert CorBENzL, Germany, (Hochst.) 
Gray dye. Diethyl amino naphth phenoxazin sulfo. 


Nitroso diethyl ANILIN, 1 mol., and 1 mol. 2-NAPHTHOL 6-sulfo “Schaeffer” heated at 100° 
in glac. acetic or alcohol, or in aq. with ZnCl, at 70-80°. Blue-cray basic mordant dye, fast to 
light and suitable for printing. 

Sulfonated S. 649—‘“‘New Blue R.”’ 


494,838—Apr. 4, 1893. Fritz Benprer, Germany. (Leonhardt.) 
Blue dye. Tetra methyl diamino methyl phen-oxazin. 
Dimethyl 3-amino creEsor, condensed with nitroso dimethyl ANILIN or other. Buiugx basic mor- 


dant dye. 
S. 620—“Capri Blue GON.” 


234 DIGEST OF PATENTS 


497,114—May 9, 1883. Jacob Brack; Switzerland. (Durand.) 
Blue dye. (Process also claimed.) Alkyl amino derivs. of gallocyanins. 

GALLOCYANIN from GALLIC acid or other and nitroso dimethyl aniLIN, heated with mMETHYL- 
AMIN or other fatty amin. VIOLET to green-BLUE acid mordant (Cr) dye, suitable for printing. 


499,243—June 13, 18093. Emil Meyer, Germany. (Bayer.) 

Blue dye. (Process also claimed.) Dimethyl amino phen-naphth oxazin with tetra methyl 
diamino diphenylmethane substituted for alfa hydrogen (4) in naphthalene component. 
NEw BLUE R, from nitroso dimethyl ANILIN and 2-NAPHTHOL, condensed with tetra methy\ 


diamino BENZHYDROL. BLuE basic mordant dye, by heating in alc. soln. suitable for printing. 
S. 652—‘‘New Fast Blue F,”’ etc. 


518,458—Apr. 17, 1894. Karl KrexKELER and Paul Krais, Germany. (Bayer.) 
Blue dye. (Process also claimed.) Amid of diethyl gallocyanin. 

Nitroso diethyl an1L1n boiled in alc. or acetic soln. with GALLAMIc acid. Brive to blue-vioLEer 
acid mordant (Cr) dye. 

S. 641—‘‘Corein RR powd.” Similar to Bierer’s patent, see second part of method S. 641. 


§24,235—Aug. 7, 1894. Oscar Batty, Germany. (Badische.) 
Blue dye. (Process also claimed.) Gallocyanin. (?). 


Ga.Lic acid and dimethyl an1L1Nn or other, 2 mols., in dry condition, mixed with POCI,, then 
ZnCl, added. BuiveE acid mordant (Cr) dye, fast to light. 


531,148—Dec. 18, 1894. Joseph BiererR and Charles De La Harpr, Switzerland. (Durand.) 
Blue dye. (Process also claimed.) A naphthol deriv. of gallocyanin similar to the resorcin 
deriv. S. 642. ‘‘Phenocyanin.” 


GALLOCYANIN from nitroso dimethyl] ANILIN and GaLLic acid, or other, combined in acid soln. 


with 2-NAPHTHOL 6-sulfo, oxidized in alk. soln. by air, then reduced in carbonate soln. by bisulfite. 


Buus and blue-vioLetT acid mordant (Cr) and acid dyes. 
S. 645—‘‘Gallazin A’ etc. See discussion of formula of this product in 992,613, which 
combines in alk. soln. 


534,809—Jan. 26, 18905. Joseph Birerer, Switzerland. (Durand.) 


Blue dye. (Process also claimed.) Mono-, di- or tri-sulfo deriv. of the anilid of diethyl amino | 


gallocyanin. 

Diethyl amino azo BENZENE sulfo or other di-alkyl amino azo benzene sulfonated in the 
second benzene nucleus, condensed with GALLAMIc acid or other in glac. acetic soln. BLUE, VIOLET 
to GREEN acid and acid mordant (Cr) dyes, fast to light and fulling. 

S. 628—‘“Gallocyanin MS.” §S. 641—‘“‘Corein RR.” Incorrectly described in Schulz 646 
as “faction of anilin on Coreine (641) and sulfonation.”’ 


547,173—Oct. 1, 1895. Carl A. Moyer and Charles p—E LA Harpe, Switzerland. (Durand.) 
Leuco compound and process of making it. Leuco form of resorcin dimethyl 
gallocyanin. 


Nitroso dimethyl anILIN, or other, condensed with Gatiic acid or other to form GALLOCYANIN 
or amid thereof, which is heated in strong acid soln. with rREsorcIN. Lvs to blue-vioLEr acid or 
acid mordant (Cr) dyes, suitable for printing. 

S. 642—‘Phenocyanin V S.” Note 585,934 uses gallamic acid, ‘sulfonates and oxidizes in 
alk. soln. with air, while 616,622 oxidizes in alk. soln, excluding air. 


548,158—Oct. 15, 1895. Emil Exsarsser, Germany. (Dahl.) 
Green dye and process of making it. 3.4-Dioxy 4’-sulfo 1.2-dinaphth oxazin (Schulz). 


2-AMINO I-NAPHTHOL 4-Sulfo (or 1.2.4) 1 mol., condensed with 1 mol. 1.2-NAPHTHOQUINONE 
4-sulfo by heating in alk. soln., then another half mol. of naphthoquinone added to boiling soln. 
Better yield obtained by excess quinone. GREEN acid mordant dye. 

S. 656—‘‘Alizarin Green G.” 


548,344—Oct. 22, 18905. Arthur AsHwortu and Joshua Burcer, England. 
Brown dye. (Process also claimed.) 3.4-Dioxy naphth phenoxazin 1-carbo acid. 

I-AMINO 2-NAPHTHOL added to a sulfuric acid soln. of GaLiic acid, or tannin, then heated 
gradually to 85-90°. Brown acid mordant (Cr) dye, fast to light and soap. 

Note 548,345 and 46 and 548,416 (Azo) for related dyes. 


GROUP XI.—OXAZIN 235 


548,345—Oct. 22, 1895. Arthur AsHwortH and Joshua BurceEr, England. 
Brown dye. (Process also claimed.) 3.4-Dioxy naphth phenoxazin 1-carbo acid. 


Nitroso 2-NAPHTHOL or (2.1) added gradually to a soln. of tannin or GaLLic acid in cone. 
H,SO,, keeping below 25° at first, then raising temp. slowly to 90°. Addition of bisulfites to. 
color paste improves it. Brown to almost BLAcK acid mordant (Cr) dye, fast to light and soap. — 


585,934—July 6, 1897. Charles p—E LA Harpe, Switzerland. (Durand.) 
Bloue dye. (Process also claimed.) Amid of resorcin diethyl gallocyanin sulfo acid. 


Nitroso diethyl ANILIN or other condensed with GALLAMIc acid or any gallic acid deriv. to 
GALLOCYANIN, and this condensed with rEsorciNn, then sulfonated before or after oxidation in alk. 
soln. with air. Brug acid and acid mordant (Cr) dyes, suitable for printing. 

S. 643—‘‘Phenocyanin T V.” Note 547,173 and 616,622 for modifications. Schulz 643 re- 
ports dye process as “Heating of phenocyanin (642) with sulfites.” 


613,578—Nov. 1, 1898. Charles p—E LA Harpe and Charles VaucueEr, Switzerland. (Durand.) 
Blue dye from gallocyanin and process of making same. Leuco sulfo gallocya- 

nin, 

Nitroso diethyl an1LIN or diethyl amino azo benzene condensed to a GALLOCYANIN then treated 
with bisulfite in neutral or acid soln. Buur acid mordant (Cr) dye. 

S. 631—‘‘Chromocyanin V paste.’’ Note 518,458 for gallocyanin mfr. and 638,576 for closely 
similar specifications. 


616,622—Dec. 27, 1808. Charles p—E LA Harper, Switzerland. (Durand.) 
Blue dye from gallocyanin and process of making same. 


Nitroso diethyl ANILIN or other combined with GALLAMIc acid to form a GALLOCYANIN, then 
with RESORCIN as in 547,173, and boiled in alk. soln. with exclus‘on of air. Violet BLUE acid 
mordant (Cr) dye, suitable for printing. 

-S. 644—“Ultracyanin B and R.” Apparently same as Steiner’s pat. S. 644 but ten years 
earlier. Note also 585,934 in which dye is heated_in alk. soln. with air, while above method 
excludes air. 


638,576—Dec. 5, 1890. Charles p—E LA Harpe and Charles VAucHER, Switzerland. (Durand.) 
Oxazin dye. Leuco sulfo gallocyanin. 

Same as 613,578 except slightly different proportions of ingredients used. Comparison with 
410,733 Made and different color reactions of product from those of 613,578 reported. No 
process claim. 

Near S. 631—‘‘Chromocyanin V.” 


643,338—Feb. 13, 1900. Arnold SYt5INER, Switzerland. (Sandoz.) 
Blue dye from gallocyanin. Alphyl sulfone radical substituted for H in OH of gallocya- 
nin dye. 


GaLLOcYANIN HCl stirred into soda-soln., heated to 70° and BENZENE sulfo chloride slowly 
added. Buve acid, acid mordant (Cr), and developed (CrO,) dyes, fast to light and milling 
when chromed, 


654,087—July 17, 1900. Bruno Bryer and Friedrick SCHAARROSENBERG, England. (Badische.) 
Blue-green oxazin dye. Possible tetra methyl triamino oxy phenoxazin. 

Nitroso diethyl 3-amino PHENOL HCl or other heated at 100° in aq. soln. with SnCl,, pptd. 
with HCl and Na salt formed as usual. Blue-creEN acid mordant dye, suitable for lakes, fast to 
milling and light. 


662,224—Nov. 20, 1900. 
Charles p—E LA Harpr, Charles VAucHER and Herman Loretan, Sw’'tzerland. (Durand.) 

Gallocyanin sulfite dye and process of making same. Probably a bisulfite comp. | 

of a sulfo gallocyanin anilid that may be further sulfonated. 

Nitroso dimethyl an1L1In condensed with CALLANILID to form GALLOCYANIN, sulfonated, then 
heated with bisulfite. Buus acid mordant (Cr) dye, suitable for printing. 

S. 633—‘“Indalizarin R.” Note 613,578 and 638,576 which also apply bisulfite to a sulfonated 
gallocyanin. 

16 


236 DIGEST OF PATENTS 


663,221—Dec. 4, 1900. Charles pE LA Harpe, Switzerland. (Durand.) 
Leucogallocyanin-sulfonic acid and process of making same. Leuco gallocya- 
nin sulfo acids, dyeing chromed cotton blue, discharging white. 

Leuco dye from GALLAMIC acid and nitroso dimethyl AaNnILIN, or other, (‘‘Corein 2 R,” 
“Gallamin Blue,’ ‘‘Prune,” etc.) slowly added at ordinary temp. to sulfuric acid (100 per cent) 
and let stand. Chlor sulfonic acid also can be used to advantage. 

Note 534,809, 629,666 and 663,220. 


707,832—Aug. 26, 1902. Charles pE ta Harps, Switzerland. (Durand.) 
Blue dye and process of making same. A sulfonated alkyl benzyl gallocyanin. 
Nitroso alkyl benzyl aniLin sulfo condensed with Gatiic acid or derivatives. BuLusg acid mor- 
dant (Cr) dye. 
S. 625—‘‘Chromheliotrop. sulf.” 


707,833—Auzg. 26, 1902. Charles p— LA Harpe, Switzerland. (Durand.) 


Blue dye and process of making same. _ Resorcin deriv. of sulfo ethyl benzyl gallo- 
cyanin amid. 
Nitroso ethyl benzyl aniLin sulfo condensed with GALLAMIc acid to form GALLOCYANIN then 
condensed with RESORCIN in acid soln. Brug acid mordant (Cr) dye. 
Near S. 642—‘‘Phenocyanin V S” sulf. 


807,181—Dec. 12, 1905. 
Charles Oswatp, Herman Loretan and Charles p— La Harper, Switzerland. (Durand.) 
Yellow-green dye and process of making same. Formaldehyde deriv. of dimethyl 
gallocyanin amid. 

GALLOCYANIN dye, from nitroso dimethyl ANILIN and GaLLAmic acid, or other, and FORMALDE- 
HYDE, heated in dil. HCl at 100°, or in conc. H,SO, at room temp., then pptd. by alkali. Sub- 
sequent heating in aq., dil. acid or aq. CaCl, etc. at 100° or higher, gives a blue dye. Yellow- 
GREEN and BLUE acid mordant (Cr) dyes. 


842,303—Jan. 29, 1907. 
Charles p—E LA Harpe and Rudolf BurckuHarpt, Switzerland. (Durand.) 
Leuco products from gallic compounds and alkyl-diamino-arylIthiosulfonic 
acids, &c. (Process also claimed.) Thio sulfonated amid of dimethyl gallocyanin. 


Dimethyl 4-PHENYLENE DIAMIN thio sulfo or diethyl compound condensed with GaLLamic acid, 
gallic acid, methyl gallate or gallanilid. Blue-vioLer acid mordant (Cr), fast to light and washing. 
Near S. 637—‘‘Gallamin Blue” or 641 ‘‘Corein.” 


844,156—Feb. 12, 1907. Herman Loreran, Switzerland. (Durand.) 


Greenish-blue dye and process of making same. Dimethyl gallocyanin amid, in 
which H and OH are substituted by diamins. 


Nitroso dimethyl ANILIN, or other, and GALLAMID, methyl gallate, etc., condensed to GALLo- 
CYANIN, then heated at 70° with dimethyl or diethyl 4-PHENYLENE DIAMIN, or 3-phenylene diamin 
or other aromatic diamin with one free amino group, and with dinitro benzene or other nitro 
body. Green-BLUE acid mordant (Cr) dye. 

S. 627—‘*Modern Cyanin.” 


856,536—June 11, 1907. William LomMMmEL, Germany. (Bayer.) 
Leueco derivative from gallocyanin. Leuco gallocyanins by alkaline reduction and 
condensation to pyrogallol. 
Dye of 856,537 heated for long time with alkaline reducing agents until after oxidation 
it is insol. in dil. Na,CO, and sol. in HCl with blue color. Pyrogallol condensation as in 856,537, 
and reduction to leuco form take place in one operation. VuioLEer acid mordant (Cr) dye, suitable 
for printing, more sol. than original gallocyanin. (No claim for dye.) 


856,537—June 11, 1907. Wilhelm Lommet, Germany. (Bayer.) 


Gallocyanin dye. Pyrogallol deriv. of gallocyanin. 

GALLOCYANIN from nitroso dimethyl ANILIN and GaLiic acid heated with ag. sod. acetate 
until sol. in HCl and insol. in alk. carb. soln. VuioLet acid mordant dye, suitable for printing, 
of redder and purer shade than original gallocyanin. No claims as dye. 


GROUP XI.—OXAZIN 237 


Note 856,536 and 884,745 for leuco form and also 863,907 and 629,666 for similar processes 
using sodium acetate. 


863,907—Aug. ‘20, 1907. Charles pe 1A Harpz, Switzerland. (Durand.) 
Process of making leuco gallocyanin. Leuco gallocyanin corresponding in pyrogallol. 


Nitroso dimethyl ANILIN and GALLIC acid condensed to GALLOCYANIN, heated in vat or auto- 
clave in water to 100°, with or without an alkali, and alkali acetate or sulfate. VuioLEt acid 
mordant (Cr) dye, suitable for printing. 

S. 624—‘‘Modern Violet N.” Patent is process classed as dye. Note 629,666 and 884,745 
for leuco gallocyanin and 856,536-7 for similar process using sodium acetate. 


884,745—Apr. 14, 1908. Wilhelm LommeEt, Germany. (Bayer.) 
Leuco derivative of the gallocyanin series. Pyrogallol derivs. of amino gallocya- 
nins. 


Celestine Blue S. 641 or Gallamin Blue S. 637, heated in vat or autoclave with a) glycerin 
to 150°; b) water to 125°; or with c) alcohol to 140°. 
Note 410,733, 534,809 and 863,907, etc. 


893,855—July 21, 1908. Wilhelm LomMeEL, Germany. (Bayer.) 
Leuco derivative of the gallocyanin series. (Process also claimed.) Leuco derivs. 

of substituted gallocyanins. 

“Celestin Blue,” derived from nitroso dimethyl ANILIN and GALLAMINIC acid, 2 parts, added 
to heated mixture of 1 part phenyl GLycin and 2 parts glycerin, at 115°, then dissolved in dil. 
HCl. Or without glycerin, mixture can be boiled in dil. HCl. Other components claimed. Buius 
to VIOLET acid mordant dyes. 

Near S. 637—‘‘Gallamin Blue paste.” 


895,635—Aug. 11, 1908. Carl Hemwenreicu and Eduard Martz, Germany. (Bayer.) 
Gallocyanin dye. Amid of chlor diethyl gallocyanin. 


4-Nitroso 3-chlor diethyl anrL1n condensed with GALLAMiIc acid. Green-B1uE acid mordant dye. 
Chlor deriv. of S. 641—-“Corein R R.” Note 534,809 for S. 641. 


897,619—Sept. 1, 1908. Charles p—E LA Harpe, Switzerland. (Durand.) 
Process of condensing gallocyanins with amins. Anilid of dimethyl gallocyanin. 
Improved process for condensing amins with gallocyanins. (General claims.) 


Nitroso dimethyl anin1in or homolog, condensed with Gatuic or gallamic acid to form 
GALLOCYANIN then with ANILIN or other amin in presence of nitrobenzene or other, to prevent 
reduction and secure full yield of anilid deriv. Buiug acid mordant dyes. 

Near S. 522—‘‘Delphin Blue.” 


898,0389—Sept. 8, 1908. 
Charles pz 1A Harpr, Rudolf BurcKHarpt and Ernst ZEHNTNER, Switzerland. (Durand.) 
Gallocyanin dye and process of making same.  Dialkyl gallocyanin sulfo acids 
(general claim.) 


Nitroso dimethyl ANILIN or other nitroso alkyl amins or sulfo acids of same, condensed with 
PYROGALLOL sulfo or other related sulfo compound. VuioLET to BLUE acid mordant dyes. 
S. 633—‘‘Pyrogallocyanin, Sulfo Acid.” Note 898,040 for unsulfonated mono alkyl comp. 


898,040—Sept. 8, 1908. 
Charles p—E LA Harrse and Rudolph BurcKkuHarpt, Switzerland. (Durand.) 
Gallocyanin and process of making same. Mono alkyl gallocyanins (general claims). 
Nitroso ethyl an1Lin or other nitroso mono alkyl arylamin or amid thereof condensed with 
GALLIC acid or derivs. VroLet acid mordant dye. 
S. 625—‘‘Chromheliotrope.” Original patent makes no reference to ‘“‘reduction” of product. 
Schulz tables call for this subsequent process. 


898,098—Sept. 8, 1908. 
Charles p—E 1A Harper, Karl Oswatp and Ernst ZEHNTNER, Switzerland. (Durand.) 
Condensaton dye from gallocyanins and process of making same. Leuco 
form of methyl deriv. of dimethyl gallocyanin anilid. 
Nitroso dimethyl aNILIN, ANILIN and methyl Ganiic acid condensed to GALLOCYANIN anilid, 


then reduced in acid soln. with Zn dust. Brive acid mordant dye, used for printing. 
Near S. 640—‘‘Modern Azurin DH.’” 


238 DIGEST OF PATENTS 


898,842—Sept. 15, 1908. 
Charles p—E LA Harpe and Rudolf Burcxuarpt, Switzerland. (Durand,) 
Gallocyanin dye and process of making same. 


Product from condensation of nitroso diethyl ANILIN with GALLAMID is heated in autoclave 
at 110°-130° with 2 parts alcohol, 0.17 parts DINITROBENZENE and 3.33 parts 15 per cent alc.-NH, 
and separated product converted to HCl salt of leuco deriv., which is sol. in aq., in cone. H, So, 
(RBr) and is a green BLUE acid mordant (Cr) dye. 

S. 638—‘‘Amido Gallocyanin Blue.” 


901,65 7—Oct. 20, 1908. Arnold STEINER, Switzerland. (Sandoz.) 


Gallecyanin dye and process of making same. Quinhydrone formed by action of 
a gallocyanin on a leuco gallocyanin. 


GALLOCYANIN from nitroso dimethyl ANILIN and GaALLic acid suspended in dil. HCl and Zn 
dust equivalent to 0.5 mol. added slowly. Or a leuco gallocyanin is partly oxidized by ammonium 
persulfate, or other. Or equimolecular amounts of a gallocyanin and leuco gallocyanin are heated 
at 50° in dil. HCl. Any mixed combination may be made. Vu1oLEtT acid mordant dye. 

S. 632—“Ultra Violet L, G P.’ 


902,154—Oct. 27, 1908. Wilhelm LommeEt, Germany, (Bayer.) 
Celestin-blue sulfonic acid. Sulfa acid of diethyl gallocyanin amid. 

“Celestin Blue,” from nitroso diethyl ANILIN and GALLAMIC acid added to 4 parts cooled 
chlor sulfonic acid then heated to 90°. Brus acid mordant dye. 

Near S. 637—‘“‘Gallamin Blue.’”’ Addition to 663,221. 


929,350—July 27, 1900. Charles VaucHER, Switzerland. (Durand.) 
Leueo derivatives of gallocyanin arylids, &c., and process of making same. 

Producing stable leuco forms* of gallocyanin arylid or sulfo derivs., that may be fixed on 

mordant cotton by short steaming. 

GALLOCYANIN anilid obtained by condensing anilin with product from nitroso dimethyl 
ANILIN and GALLAMID, boiled in dil. alc. soin. while HCl and formaldehyde hydrosulfite are 
gradually added in absence of excess free acid sufficient to split off amino-aryl group. Other 
components claimed. BuLur acid mordant dyes. 


S. 630—‘‘Cyanazurin.”’ 
* Classed by Schulz as dyes. 


936,247—Oct. 5, 1909. Wilhelm LommeEL, Germany. (Bayer.) 

Gallocyanin dye and process of making. Sulfonated anilins diethyl gallocyanin. 
Nitroso diethyl ANILIN and GaLLic acid condensed to GALLOCYANIN, then combined with 

ANILIN or other, oxidized, carbo group split off and then sulfonated. Green BLUE acid mordant 

_ (Cr) dyes, used for printing. 

S. 622—‘“‘Chrom Azurin” see footnote. This patent covers specific claims, for general 

claims see 926,248. : 


936,248—Oct. 5, 1909. Wilhelm Lommet, Germany. (Bayer.) 
Gallocyanin dye and process of making same. Gallocyanin aryl amids. 


GALLOCYANIN or derivs., condensed with ANILIN or other amin at common temp. by passing 
air through mixture. Green BLUE acid mordant (Cr) dyes, suitable for printing. 
Note Ser. 466,489. 


955,040—Apr. 12, 1910. Charles Barsezat, Switzerland. (Durand.) 


Derivatives of gallocyanins and process of making. To obtain oxy gallocyanin 
without reduction to leuco dye. 

Anilino CELESTIN BLUE (diethyl GALLOCYANIN) heated in 37 per cent H, SO, to 75°, diluted, 
filtered hot. Other gallocyanin dyes are heated as above, varying acids, temps., concentration, 
etc. to suit dye. Tests for end of reaction are given. BuLuk acid mordant dye. 

Note 698,098 for leuco non hydroxylated dye. 


961,361—June 14, 1910. Wilhelm Lommet, Germany. (Bayer.) 


Leuco derivative of diethylgallocyanin. A leuco decarboxylated diethyl gallocyanin 
by improved process. 


Nitroso diethyl ANILIN and GaALLIc acid condensed to form GALLOCYANIN as in 961,362, re- 


GROUP XI.—OXAZIN 239 


duced with Zn and HCl, filt. and heated to 95-100° some hours, preventing access of air, till 
soluble in acid and insol. in carbonate solns. Brug acid mordant dye. 
Note 961,362 for same dye by another process. 


961,362—June 14, 1910. Wilhelm LomMMmeEL, Germany. (Bayer.) 
Galloeyanin dye. Decarboxylated diethyl gallocyanin. 


Nitroso diethyl aninin and GaLLic acid condensed and boiled with alkali till soluble in 
acid. Buiugr acid mordant dye. 
Note 961,361 for leuco form by another process. 


962,712—June 28, 1910. Wilhelm Lommet, Germany. (Bayer.) 
Leuco diethylgallocyanin. Leuco form of diethyl gallocyanin carbo acid, No. 253,721. 


Nitroso diethyl anin1n and Gatiic acid condensed to form GALLOCYANIN then reduced 
electrolytically, by Zn and HCl or by other means. 

S. 635—‘“‘Blue 1900, FC.” This appears to be a duplication of 639,666, (Harpe, 18099) 
which includes diethyl gallocyanin leuco comp. or of 257,498 which reduces with Zn. in alk. soln. 


985,424—Feb. 28, 1911. Wilhelm Lommet, Germany. (Bayer.) 
Oxazin dye. 


GALLAMIC acid heated in 60° sulfuric acid with 4-nitroso PHENOL slowly to 70°. Product 
gives leuco comps. on reduction, modified leuco comps. with SO, or its salts, which latter are 
further modified by acids, all of which form chrome lakes. Brown to vioLeT acid mordant (Cr) 
dyes, suitable for printing, fast to washing, Cl. 


992,613—May 16, 1og11. Arnold StTEe1nER, Switzerland. (Sandoz.) 
Process for the manufacture of coloring-matters derived from gallocyanin. 
Decarboxylated naphthol dimethyl amino gallocyanin. (Product also claimed.) 


GALLOCYANIN, from nitroso dimethyl anit1n and catuic acid, or other, condensed with 
RESORCIN, naphthol sulfo, or other in alk. soln. in presence of an oxidizing agent. Leuco form 
is made by reduction with Zn in acid soln. or by bisulfites in alk. soln. BLur to vioLer acid mor- 
dant (Cr) dye. 

S. 644—‘“Ultracyanin B.” 


1,000,899—Aug. 15, 1911. 
Charles p—E tA Harpe and Rudolf Burckuarpt, Switzerland. (Durand.) 
Leuco dyestuffs of the gallocyanin series and process of making same. 
Leuco gallocyanin benzyl amin compounds. 


GaLLocyaNIN, from nitroso dimethyl aninin and Gatiic acid, condensed in alc. soln. at 
50° with benzyl ANILIN, in presence of air or easily reducible comp. Product is reduced to 
leuco form or is dissolved and boiled in aq. Na,CO, soln. to decarboxylate then reduced. 
Green BLUE acid mordant (Cr) dye. 

Note 697,610 for use of air or nitrobenzene to prevent reduction during condensation. 


1,028,045—May 28, 1912. Hans MAnsFIELD, Germany. (Badische.) 
Gallocyanin compounds and process of making them. Leuco form of gallocyanin 
compounds with dioxy tartaric acid, etc. 
Prune S. 636, a GALLOCYANIN from nitroso dimethyl anin1in and methyl Gatiic acid, or 
other, and dioxy TarRTaRIc acid or tartronic acid heated in acid soln. Brur acid mordant dye. 


1,065,063—June 17, 1913. Rudolf Maac and Paul Jorc, Germany. (Hochst.) 
Benzoquindne derivatives and process of making same. 1.4-Dichlor 4',4”- 
diethoxy triphen dioxazin and derivs. 
CHLORANIL condensed with 4-PHENETIDIN by boiling in alcohol to form 4.4/-diphenetidin dichlor 
BENZOQUINONE and product boiled in nitrobenzene with sublimed FeCl,. Red powds. insol. 


aq. and alc., sol. in conc. sulf. (B) in boiling xylene (B-Y flour); fast violet RED pigment or 
lake dye. 


1,138,670—May 11, 1915. Georg KrANZLEIN and Rudolf Hacenspacu, Germany. (Hoéchst.) 
Arylaminoanthraquinone dyestuffs and process of making same. _1-Toluidin 
4-0xy 2.3-anthraquinone phenyl oxazin. 
OxazoL.E derived from 2-amino ALIZARIN and BENzOYL chloride or other, nitrated or 
chlorinated and condensed with 4-roLvIpIN or other, then sulfonated. Or oxazole first sulfonated, 


240 DIGEST OF PATENTS 


then nitrated and condensed with amino-sulfo group in another nucleus. VioLEtT and GREEN acid 
and developed (CrO,) dyes. 


1,188,259—June 20, 1916. Gadient Encr and Fritz GriksHABER, Switzerland. (Basle.) 
Leuco derivatives of sulfureted gallocyanins and process of making same. 
Leuco form of thio gallocyanins, 


GALLOCYANIN sulfur compound, derived from nitroso dimethyl ANILIN, GALLAMIC acid and 
Na,S, or other, reduced in acid soln. to form stable leuco dye compound. Buivug acid mordant 
(Cr) dye, suitable for printing, fast to washing, light. 

Near S. 631—‘‘Chromocyanin.”” Patent emphasizes that leuco compound is stable. 


1,199,458—Sept. 26, 1916. Gadient Enc1, Switzerland. (Basle.) 
Halogen derivatives of gallocyanin dyestufis and process of making same, 
Leuco form of amid of brom dimethyl amino gallocyanin. 
GALLAMIN BLUE, derived from nitroso dimethyl ANILIN and GALLAMIC acid, or other gallo- 
cyanin, brominated or chlorinated in sulfuric acid soln. with NaBr or Br, etc., then reduced 
to leuco form for printing. Buus acid mordant dyes, faster to washing, light and Cl. than parent 
dyes, suitable for printing. } 


1,268,455—June 4, 1918. Armin Gros and Jakob WurRGLER, Switzerland. (Basle.) 
Condensation product of gallocyanin dyestuffs with amins and process of 


making same. Anilin gallocyanin or other. 

GALLOCYANIN HCl mixed with ANILIN poured into strong peroxid soln. then heated at 100°. 
Other components and peroxids claimed. Green BLUE acid mordant dye, suitable for printing. 

Near S. 639 or 640. 


1,299,070—Apr. 1, 1919. Emil WALDER, Switzerland. (Sandoz.) 
Manufacture of blue to greenish-blue coloring-matters of the gallocyanin 
series. Leuco gallocyanin amino aryl amid comp. 


3- or 4-Amino BENZAMID heated with CELESTIN BLUE, or other gallocyanin at 100°, with or 
without oxidizing agent such as air or aromatic nitro comps. Alc. soln. can be used. Leuco 
comps. are formed by reduction with Zn and HCl, by hydrosulfite, etc. Bruxr to green BLUE acid 
mordant dyes, fast to light, soap and chlorine. 


Group XII.—PYRAZOLONE. 


324,630—Aug. 18, 1885. H. Z1EGLER, Switzerland. (Badische.) 
Coloring-matter from phenylhydrazine. (Product.) 4’-Sulfanilic acid 4-azo 4”-sulfo- 
phenyl pyrazolone 3-carbo acid. 

Dioxy TARTARIC acid, Na salt, is heated at 40° in acid soln., filt., then heated at 80° in alk. ; 
soln. with 2 mols. phenyl HyDRAzIN sulfo acid. Product is sol. in aq. (Y), and in cone. H,S0O, 
(Y), almost insol. boiling alc. or glac. acetic acid, aq. soln. becomes redder with NaOH, conc. aq. 
soln. pptd. by alc., soln. with Pb (NO,), ppts. (OQ), with BaCl, ppts. (RO), with acid or alk. 
reducing agents is decol.; a YELLOW acid dye. 

S. 23—‘‘Tartrazin.” 


627,690—June 27, 1899. J. Herpasny, Germany. (Oehler.) 
Yellow wool dye and process of making same. 4’/Sulfanilic acid 4-azo 4’-nitro 
phenyl pyrazolone 3-carbo acid. 

Oxalo-acetic ester, heated at 45-50° with 4-nitro PHENYL hydrazin in dil. sod. acetate soln., 
then at 90-100° in alk. soln. Separated 4-nitro phenyl PpyRAZOLONE carbo acid: is coupled with 
1 mol. diazotized sulfanilic acid. Orange yellow powd., easily sol. aq. (Y-O), greener with 
acids, darker with NaOH, slightly sol. 90 per cent alc. (Y), sol. conc. H,SO, (YBr); a green 
YELLOW acid dye, fast to milling. 

S.  23—“*T'artrazin.” 


. 
~ 
; 
i 
8 
5 
; 
| 
4 
4 
§ 
..: 
2 


656,857—Aug. 28, 1900. Franz ScHoLL, Germany. (Hochst.) 
Yellow dye and process of making same. Sulfo primulin azo phenyl methyl pyrazo- 
lone. 

PRIMULIN sulfo is diazotized and coupled in alk. soln. with phenyl methyl Pyrazotonge. A 
yellow-brown powd., easily sol. hot aq., (Y), fairly sol. alc., insol. ether, petroleum and benzene, 
sol. conc. H,SO, (Y), aq. soln. pptd. by mineral acids as gel; a direct yELLOW dye. 

S. 26—‘‘Dianil Yellow R.” Note 656,858 and 59. 


GROUP XII.—PYRAZOLONE 241 


656,858—Aug. 28, 1900. F. Scuoii, Germany. (Hoéchst.) 
Orange dye and process of making same. Sulfo primulin azo 4’-sulfo phenyl pyra- 
zolone carbo. acid. 


PRIMULIN sulfo is coupled with 4-sulfo phenyl PyRAZOLONE carbo acid. An orange-red powd., 
easily sol. cold aq. (OY), almost insol. alc., insol. ether, benzene and petroleum, sol. conc. 
H,SO, (OY), pptd. from aq. soln. by acids; a direct orRANGE dye, fast to acid, alk., and light. 

Near S. 27—“Dianil Yellow 2R.’’ Note 656,857. 


656,859—Aug. 28, 1900. F. Scuoiit, Germany. (Hdéchst.) 


Yellow azo dye and process of making same. Sulfo primulin azo 4’-sulfo phenyl 
methyl pyrazolone. 


PRIMULIN sulfo is coupled with 4-sulfo phenyl methyl pyrazotonre. An orange yellow powd., 
easily sol. cold aq. (OY), diff. sol. alc., insol. benzene, petroleum and ether, pptd. from aq. 
soln. by acid; a direct YELLOW dye, fast to acid, alk. and light. 

S. 27—‘Dianil Yellow 2R.” Note 656,857. 


658,593—Sept. 25, 1900. F. Scuoii, Germany. (Hochst.) 


Green-yellow dye and process of making same. Primulin azo aceto acetic acid, 
ethyl ester. 


Primulin sulfo or xylidin deriv. is coupled with aceto acetic acid, ethyl ester, or other 
aliphatic beta diketones. Or primulin bases and aceto acetic acid may be coupled first and 
then sulfonated. Yellow powds., easily sol. aq. (Yt), soln. not changed by dil. acids or alks., 
darkened by strong alk., soln. conc. H,SO, (Y); direct green yELLOow dyes for cotton and acid 
dyes for wool. 

S. 25—‘‘Dianil Yellow 3G.” 


679,172—July 23, 1901. Paul Juxtius, Germany. (Badische.) 
Orange dye and process of making same. 


Oxalyl acrtic ester with 2-tolyl Hyprazin HCl or other, in xyYLENE soln. is condensed at 
100° and saponified to form 2-tolyl PyRAZOLONE carbo, or other, which is combined with diazo 
PRIMULIN sulfo. Product is diff. sol. in cold aq. (O), redder with NaOH, reduced with Zn dust 
in NaCl soln. yields primulin sulfo acid; orANGE developed dye, fast to soap, alk. carb., acids and 
light. 

Near S. 26—‘“‘Dianil Yellow.” 


731,670—June 23, 1903. W. DotiFus and R. HacEnpacu, Germany. (Héchst.) 
Yellow monoazo dyestuff rand process of making same. 4-Sulfo anthranilic acid 
azo phenyl methyl pyrazolone. 
4-Sulfo ANTHRANILIC acid is coupled in alk. carb. soln. with phenyl methyl PyRAZOLONE. 


A yellow powd., sol. hot ag.; a YELLOW dye suitable for lakes, fast to aq., acid, lime and light. 
S. 28—‘‘Pigment Fast Yellow.” 


808,919—Jan. 2, 1906. J. Hacenzpacyu, Switzerland. (Geigy.) 
Red azo dye and process of making same. Amino naphthol sulfo phenyl methyl 
pyrazolon. 


1-Amino 2-NAPHTHOL 4-sulfo, or other ortho amino naphthols is coupled with phenyl methyl 
PYRAZOLONE or other pyrazolone free to combine in position 4. Dark brown powds. with metallic 
luster, sol. in aq. (OY-RBr), with acetic (YR-BR), sol. conc. H,SO, (O-R); yellow-srown to 
violet brown acid dyes, becoming orange RED to violet red when after chromed. 

S. 29—‘“‘Eriochrome Red B.”’ 


935,370—Sept. 28. 1909. P. Jutius and E. Fusseneccrer, Germany. (Badische.) 

Pyrazolone dyes and process of making them. A pyrazolone dye in which 3-chlor 
5-sulfo 2-toluidin substitutes N-hydrogen in position 1 of the ring, or constitutes the azo 
rest, or occupies both positions. 

Dioxy TARTARIC acid, Na salt, heated in aq. to 50° then 70-80° with 2 mols. of 3-chlor 5-sulfo 
2-tolyl hydrazin. Or 3-chlor 5-sulfo 2-roLuIpDIN may be coupled with 4/-sulfo phenyl PyRAZOLONE 
carbo acid in alk. carb. soln. Yellow powds., sol. in aq. (Y-YG); YELLOW acic dyes for wool or 
for yellow lakes, fast to light. 

S. 24—“‘Pigment Fast Yellow R.” 


242 DIGEST OF PATENTS 


935,880—Oct. 5 1909. P. VoLKMANN, Germany. (Bayer.) 
Yellow azo dye. 4”-Toluidin, or other toluidin, azo 4’-sulfo phenyl methyl pyrazolone. 


4-TOLUIDIN, or other toluidin, is coupled with 4’-sulfo phenyl methyl PyrazoLONE or other 
pyrazolone. Or unsulfonated dye may be sulfonated after coupling. Yellow powds., sol. in 
aq. (Y), acid reduction yields original amin, sol. conc. H,SO, (Y); yELLow acid dyes of great 
tinctorial power, and fast. 

S. 21—‘Pigment Chrome Yellow L.”’ Note 935,830 and 969,428. 


935,880—Oct. 5, 1909. P. VotKmMANN, Germany. (Bayer.) 
Azo dye. (Product.) 2”-Toluidin 5’’-sulfo azo 4’-sulfo phenyl methyl pyrazolone. 


2-TOLUIDIN 5-sulfo, or other toluidin sulfo acid, is coupled with 4'-sulio phenyl methyl 
PYRAZOLONE or other sulfo aryl methyl pyrazolones. Or nonsulfonated pyrazolon may be coupled 
and later sulfonated. Yellow powds., sol. in aq. (Y), sol. conc. H,SO, (Y), giving the usual 
azo separation upon acid reduction; yELLOow acid dyes, level, fast to light, and of great tinctorial 
power. 

Near S. 23—‘‘Tartrazin.” 


969,428—Sept. 6, 1910. P. VotKmann, Germany. (Bayer.) 
Greenish-yellow dye. (Product.) 2”-Sulfo-anilin azo 2/-sulfo phenyl pyrazolone carbo 
acid. 


Phenyl HypRAzIN 2-sulfo, 2 mols., condensed with 1 mol. dioxy TartTaric acid, Na salt, by 
boiling 2 hours in aq. containing H,SO, to neutralize the sodium present. A yellow powd., sol. 
conc. H,SO, (Y), giving usual azo reduction products with SnCl, and HC!; a green YELLOW acid 
dye, fast to light. 

Isomer of S. 23—‘‘Tartrazin.”” Note 972,951, which employs mixed ortho and para derivs. 
of first component. 


972,951—Oct. 18, 1910. _ ~P. VouKmann, Germany. (Bayer.) 
Yellow dye. Mixture of tartrazin and 2-sulfo isomer. 


Phenyl uyprazin sulfo (0o- and p- sulfo mixed), 2 mols., condensed with 1 mol. dioxy. 
TARTARIC by boiling 2 hours in aq. soln. with sufficient H,SO, to neut. Na present. A yellow 
powd., sol. conc. H,SO, (Y); a green YELLOw acid dye. 

Near S. 23—‘‘Tartrazin.”” Note 969,428. 


982,050—Jan. 17, 1911. Hugo GELDERMANN, Germany. (DBerlin.) 


Yellow pyrazolone dye for wool. 2”-Chlor anilin azo 2/-chlor 5’-sulfo phenyl methyl 
pyrazolone. 


2-Chlor anILIn coupled with aceto acETic ester, then condensed with 2-chlor 5-sulfo phenyl 
HYDRAZIN, or pyrazolone ring first condensed, then coupled. A yellow powd., sol. in aq. and — 
alc., sol. conc. H,SO, (Y), pptd. on diln., pptd. by acid, with NH, or NaOH redder, neut. soln. 
decol. with Zn becomes violet with air; a fast yELLow acid dye. 

Isomer of S. 22.” Xylene Yellow 3 G.” 


a ee 


988,870—Aug. 4, 1911. H. GeLpERMANN, Germany. (Berlin.) 


Yellow monoazo dye and process of making same. (Product only claimed.) 
2”-Chlor anilin azo 4’-nitro phenyl methyl pyrazolone. 


a) 2-Chlor ANILIN is coupled with 4-nitro phenyl methyl PyRazoLoNE, or b) diazo 2-chlor 
anilin may be coupled with aceto acrtTic ester, then condensed with 4-nitro PHENYL hydrazin. A 
yellow powd., insol. in aq., alc., linseed oil varnish, diff. sol. benzene (OY), sol. conc. H,SO, 
(Y), pptd. on diln., decol. by Zn dust, with air (Rt); suitable for yELLOw lakes, fast to light. 


1,010,919—Dec. 5, 1911. Paul Juuius and Ernst FussENEcGER, Germany. (Badische.) 
Pyrazolone dyes and process of making same. _ 6/-Brom 4/-sulfo 2/-tolyl azo 4- 
pyrazolone carbo acid azo 6”-brom 2”-toluene 4’’-sulfo. 
Dioxy TARTARIC acid in aq. soln. with 2 mols. of hydrazin of 6-brom 2-ToLuIDIN 4-sulfo acid 


Se eS ee ee ee he ar en | ery ee 


heated gradually to 70-80°, and product salted out. Or 1 mol. diazo deriv. of first component 
is coupled in alk. soln. with 4’-sulfo phenyl PyRAZOLONE carbo acid. Yellow powds., sol. in aq. 
(Y-GY), splits at azo bond when reduced with SnCl,; yeLLow acid dyes forming lakes fast to 
light. 

Near S. 23—Halogenated homolog of Tartrazin. 


GROUP XIII.—QUINOLIN 243 


1,026,257—May 14, 1912. Karl Evset, Germany. (Kalle.) 
Manufacture of a new pyrazolone-azo dye. Chlor 1”-amino 2”-naphthol 4’-sulfo 
phenyl methyl pyrazolone. 


1-Amino 2-NAPHTHOL 4-sulfo, chlorinated in sulfuric acid soln., neut. and condensed in 
alk. soln. with phenyl methyl pyrazotonr. A red powd., sol. in aq. (OR), becoming bluer with 
alk., sol. conc. H,SO, (VR); a red orancr acid dye which becomes violet RED when after chromed. 


Near S. 29—‘“‘Erio Chrome Red.”’ 


1,098,600—June 2, 1914. P. VoLtKMANN, Germany. (Synthetic.) 
Yellow azo dyestuffs. 5”-Sulfo 2”-toluidin azo 2’-chlor 4’-sulfo phenyl methyl pyrazolone. 


2-TOLUIDIN 5-sulfo acid or other toluidin or its sulfo derivs., coupled in neut. soln. with 
aceto ACETIC ester, then condensed with 2-chlor PHENYL hydrazin-q-sulfo, by heating to 95° in 
alk. aq. Or diazo comp. may be combined with a 2-chlor aryl methyl pyrazolone sulfo acid. 
Yellow powds., sol. in aq. and conc. H,SO, (Y), azo bond split by reduction with SnCl,; green- 
YELLOW acid dyes, level and fast to light. 


Near S. 23—‘‘Tartrazin.” 


Group XIII.—QUINOLIN 


256,599—Apr. 18, 1882. C. H. Rupvo.pu, Germany. (Héchst.) 


Production of coloring-matter. (Product not process claimed.) Probably flavanilin 
admixed with diphenyl acetamidin and dimethyl quinolin (Richter). 


ACETANILID heated with ZnCl, to 230-250° with or without anittn HCl. Homologs formed 
by condensing with halogen alkyls or other. A YELLow basic dye. 


257,717—May 9, 1882. E. Jacossen, Germany. 
Manufacture of red coloring-matter. Quinolin iso quinolin benzyl methane. 


Quinolin (crude), pyridin or other, heated with Benzo trichloride with or without ZnCl, 
or other condensing agent. A RED basic mordant dye, fast to soap. 


S. 610—“‘Quinolin Red.” 


290,585—Dec. 18, 1883. E. Jacossen, Germany. 
Production of yellow coloring-matter., (Product also claimed.) Quinophthalone. 


QuINnaLDIN condensed at 190-210° with PHTHALIC anhyd by ZnCl, then sulfonated to render 
aq. sol. A YELLOW basic mordant and acid dye. 


S. 612 and 613—‘“Quinolin Yellow.” 


752,323—Feb. 16, 1904. © R. Berenpes, Germany. (Elberfeld.) 
Sensitizing dyestuff. 
QuINALDIN heated at 100° with piETHYL sulfate to form NH, comp. which is dissolved in 


warm alc. and KOH slowly added. Methods of purification given and other components claimed. 
Sensitizers in distinct parts of spectrum for photo emulsions. 


780,741—Jan. 24, 1905. R. BERENDES, Germany. (Elberfeld.) 
Sensitizing-dye. An N substituted toluquinaldin.* 
Tolu QUINALDIN 2.6-dimethyl quinolin or other, heated with ethyl ester of TOLUENE 4-sulfo 


-or other to form ammonium base then with KOH in alc. soln. A rep basic dye, used as sensi- 
tizer for photo emulsions. 


805,143—WNov. 21, 1905. FE. K6nic, Germany. (Hoéchst.) 
Cyanin dye and process of making same. 


4-Tolu QUINALDIN, methyl iodide, and 4-tolu QuinoLIN methyl iodide, condensed in boiling 
alc. soln. by adding KOH. Other components claimed. Sensitizers in red region of spectrum 
for photo emulsions. 


* According to Beacall, page 139, it is—‘‘Perikol’”? (Bayer) used for sensitizing plates to a 
maximum between wave lengths 590 to 560 uw. 


244 DIGEST OF PATENTS 


844,804—Feb. 22, 1907. B. Homoixa, Germany. (Hoéchst.) 
Blue quinolin dye and process of making the same. 

QUINOLIN, ethyl iodid, and guINALDIN, ethyl iodid, homologs or other salts warmed with 
alkali and FORMALDEHYDE, methylal or other body, then formaldehyde, alc. or other eliminated 
as solvent. A BLUE basic dye, used for sensitizing photo plates, very sensitive to light. 


S. 611—‘“‘Pinacyanol.” 


852,158—Apr. 30, 1907. A. BERTSCHMANN, Switzerland. (Basle.) 
Yellow sulfin dye of the quinophthalone series and process of making same. 
A thio phthalo naphthoquinone. 
b-Sulfo pHTHALIC acid (or disulfo) treated with PCl, to form the sulfo chloride, reduced 
with Zn to b-thio FHTHALIC acid, then heated with 2-naphtho QUINALDIN, or homologs. An 
ORANGE or YELLOW sulfide or reducing vat and developed (CrO,;) dye, which when oxidized 
on fiber is fast to washing and light, and is suitable for printing. 


890,58S8—June 9, 1908. E. Mrtyer, Germany. (Elberfeld.) 
Yellow dye. Sulfonated chlor quino phthalone. 

4-Chlor ANILIN, ACETALDEHYDE and HCl condensed to form 4-chlor QttINALDIN, heated at 
210° with PHTHALIC anhyd., and resulting chlor quino phthalone sulfonated. A green-YELLOW 
acid dye, (in alc. soln.), suitable for lakes, faster to light than those of Quinolin Yellow. 

S. 613—“‘Quinolin Yellow, aq. sol.’? (chlorinated). 


1,197,632—Sept. 12, 1916. E. Horra, Germany. (Hochst.) 
Quinophthalonesulfonie acids containing halogen and process of making 
same. Chlor iso-quino phthalone. Chlorinated in ortho position to N, thus differing from 
890,588. 
3-Chlor ANILIN condensed at 100° with PARALDEHYDE to form 2-chlor 8-QUINALDIN then 
heated at 200-210° with PHTHALIC anhyd, separated and sulfonated. A yELLOW acid dye, fast 
to light. 


S. 613—“Quinolin Yellow, aq. sol.’ 


1,338,346—Apr. 27, 1920. 
L. E. Wist, New York, and E. Q. Apams, California. (U. S. Gov't.) 
Process of making photographic sensitizing-dyes of the isocyanin type. 
Isocyanin dyes from quinolin by improved process. 
4-Tolu QUINALDIN, methiodide, or ethiodide, and 2 mols. QUINOLIN methiodide (anhydrous) 
heated in open vessel in absolute methyl alcohol, sodium methylate added, and soln. evaporated 
to 0.8 volume to cryst. dye. 


1,338,349—Apr. 27, 1920. 
E. Q. Apams, California, and L. E. Wisz, New York. (U. S. Gov’t.) 


Process of making photosensitizing-dyes effective for infra-red radiation. 
Infra-red sensitizers from quaternary halide derivs. of a, y dimethyl quinolins. 


2.4.6-Trimethyl QurINoLIN ethiodide dissolved in abs. methyl alcohol, sod. methylate added 
and let stand 2 days in open vessel at room temp. Photo sensitizing dyes in infra-red. 


1,374,871—Apr. 12, 1921. E. Q. Apams, Cal., and H. L. Hauer, Ohio. 


Photosensitizing dye of the isocyanin type. Action of strong bases on quaternary 
addition products of y methyl a-unsubstituted pyridin bases. 


Lepip1n methiodide, or deriv., heated to boil in abs. methyl alcohol, sod. methylate added, 
boiled, cooled slowly and let stand 24 hours. Other alfa methylated and gamma unsubstituted 
pytidin bases are claimed. 


1,374,872—Apr. 12, 1921. Elliot Q. Apams, California, and Herbert L. Haier, Ohio. 
Photosensitizing dye effective for infra-red radiation. 


Same process and claims as in 1,374,871, using quinolin bases instead of pyridin. 


GROUP XIV.—STILBENE 245 


1,437,674—Dec. 5, 1922. Samuel PaLx1n, Connecticut. (U. S. Govt.) 
Process of making photographic sensitizing dyes of the dicyanin type. 


2.4-Dimethyl 6-ethoxy QUINOLIN ethiodide or derived ethnitrate in soln. of Na,S in 95 per 
cent alc. (1:4) is heated at 50° or let stand at usual temp. with 4 parts CHCl,. The trimethyl 
deriv. may be used, and other quaternary addition products of alfa gamma dimethyl quigolin 
derivs. 


Group XIV.—STILBENE. 


350,229—Oct. 5, 1886. F. Benper, Germany. (Leonhardt.) 
Yellow coloring-matter. 4.4’/Diamino 2.2/disulfo stilbene disazo diphenol, or other. 

_ 4-Nitro TOLUENE heated with fuming sulf. acid to form ortho mono sulfo comp., converted 
to the Na salt, 2 mols. of which are condensed by heating with conc. NaOH to a sTILBENE, then 
reduced in acid or alk. soln. to the amino sulfo deriv., which is tetrazotized and coupled with 
PHENOL, 2 mols. salicylic acid, or other. Brown powds., easily sol. cold aq. (O), soln. turning 
red with NH, or NaOH, pptd. blackish blue by HCl, sol. conc. H,SO, (V); direct yELLow 
dyes for cotton. 

S. 303—“Brilliant Yellow’; S. 305, “‘“Hessian Yellow.’’ Note 350,230 and 395,115. 


350,230—Oct. 5, 1886. F. Benner, Germany. (Leonhardt.) 


Red coloring matter. 4.4’/-Diamino 2.2’-disulfo stilbene disazo dibeta dinaphthylamin or a 
disulfo deriv. 


4-Nitro TOLUENE, sulfonated, Na salt of sulfo comp. condensed in conc. NaOH to a sTILBENE, 
reduced to amino comp., tetrazotized and coupled with 2 mols. 2-NAPHTHYLAMIN, its 6-sulfo 
acid, or other. Brown-red powds., sol. in aq. (V) and in conc. H,SO, (B), aq. soln. with HCl 
gives blue ppt.; direct vioLer dyes for cotton. 

S. 301 and S. 302—‘‘Hessian Purple.’”? Note 350,229 and 395,115. 


360,553—Apr. 5, 1887. F. Benper, Germany. (Leonhardt.) 
Production of disulpho-acid of diamido-stilbene. Distilbene tetra ortho sulfo 

azoxy azo or disazo diamino or diphenol comp., etc. 

4-Nitro TOLUENE 2-sulfo, 2 mols., condensed in strong alk. soln., then reduced with Zn dust 
in alk. soln. or SnCl, in acid soln., tetrazotized and coupled with amines, phenols, etc. 2.2!- 
Disulfo 4.4’-diamino st1LBENE is a yellowish powd., slightly sol. aq. and alc., easily sol. alk., 
which solns. are pptd. by acids. The derived azo dyes are yELLOW direct dyes for cotton, acid 
dyes for wool. 

S. 9—“Sun Yellow.”’. Note 350,229 and 30. 


386,709—July 24, 1888. W. KELBE, Germany. (Berlin.) 
Production of coloring substances by the reaction of aromatic hydrazin 
sulphonie acids on retenchinon. Compos. probably retene disazo di-sulfanilic acid, 
or other. 
One mol. RETENQUINONE boiled in aq. soln. with 2 mols. PHENYL hydrazin sulfo acid, or 
other aromatic hydrazin sulfo acid, néut. with soda and salted out. Products are orange RED 
to violet red acid dyes, fast to soap and alk. 


395,115—Dec. 25, 1888. F. Benner, Germany. (Leonhardt.) 


Production of coloring-matter. (Product, not process, claimed.) Benzylated Cur- 
cumin S, or other. 
4-Nitro TOLUENE 2-sulfo, 2 mols., condensed to yellow dye by NaOH, as in 350,229, refluxed 
with 30 per cent NaOH, alc. and BENzyt chloride, or other. Or nitro toluene sulfo acid may 
be nitrated, brominated, alkylated, etc. Product is sol. in aq. (Y), pptd. by NaCl or BaCl, (Y), 
not reddened by NaOH; a yeELLow direct and acid dye for cotton and wool, fast to soap and alk. 
S. 304—‘‘Chrysophenine G.” Note 350,229 and 30. 


396,527—Jan. 22, 1889. F, Benner, Germany. (Leonhardt.) 
Production of coloring-matter. (Product, not process, claimed.) Azoxy azo and 
disazo distilbene tetra ortho sulfo acid. 

4-Nitro TOLUENE 2-sulfo, 4 mols., condensed and reduced by boiling in dil. alk. soln. with 
ale., glycerin, and an oxidizable substance, inorganic or organic. Part reduction gives azoxy 


246 DIGEST OF PATENTS 


azo and complete reduction the disazo form. A brown powd., sol. in aq. (Y), soln. scarcely 
altered by NaOH, pptd. by BaCl, (BrR), decol. by NaOH and Zn dust, and reoxidized by air 
(R), sol. conc. H,SO, (R-BV); a direct yELLow dye, fast to alk. and soap. 

S. 1r1—‘‘Mikado Orange G.” Note 360,553. 


455,952—July 14, 1891. C. Ris, Switzerland. (Geigy.) 
Brown dyestuff. 4.4’-Dipara-diamino diphenyl disazo 2.2 -disulfo stilbene. 


4-Nitro TOLUENE 2-sulfo, 2 mols. condensed with 2 mols. 4-PHENYLENE DIAMIN, or other, in 
hot NaOH soln. A brown powd., sol. aq. (YBr), conc. H,SO, (RV) and methyl alc., less 
sol. in ethyl alc. and glac. acetic, scarcely sol. in benzene and ether; a Brown direct dye for 
cotton, that may be diazotized and coupled on the fiber with naphthols, phenols, or amins, 
to obtain RED, BROWN, or BLACK developed colors, fast to soap. 

S: 15—‘‘Polychromin B.” 


601,063—Mar. 22, 1808. C. Ris. (Geigy.) 
Benzidin-orange. (Process also claimed.) 2.2’-Disulfo stilbene disazo di-benzidyl. 


4-Nitro TOLUENE 2-sulfo, 2 mols. condensed in alk. soln. with 1 mol. BENzIDIN, or other. 
A direct ORANGE dye for cotton. 
S. 15—‘‘Chicago Orange.” 


613,911—Nov. 8, 1808. C. Ris, Switzerland. (Geigy.) 


Yellow dye and process of making same. Diphenyl 4.4’-disazo stilbene 2.2’-disulfo 
or 4-phenyl azoxy 4/-nitroso 2.2/-disulfo stilbene. 


4.4/-Dinitro DIBENZYL 2.2/-disulfo condensed at 40-80° with ANILIN or other base of this 
series, and oxidized with NaOCl or persulfate at 60-80°. An orange-yellow powd., easily sol. 
aq. (Y), and cone. H,SO, (O), scarcely sol. alc., azo bond severed by reducing agents (Zn and 
HCl), becomes greener on treatment with hypochlorite or persulfate; green yELLOW direct dyes 
for all fibers. 

S. 12—“‘Diphenylcitronin G.”’ 


636,065—Oct. 31, 1899. C. Ris, Switzerland. (Geigy.) 


Stilbene azo dye. 4-Nitroso 2.2’-disulfo stilbene 4’-azo para amino benzene, para ethoxy 
benzene, the disazo distilbene comp., or others. 


4-Nitro TOLUENE 2-sulfo, 2 mols., condensed in hot, strong NaOH soln. with 1 mol. 4-PHENY- 
LENE DIAMIN by heating to 98°. Alkylated components are claimed and other amins, phenols 
and aryl acids containing at least one amino group. Products are sol. in aq. (Y-O) im cone. 
H,SO, (R-VR), diff. sol. alc., insol. ether and benzene, pptd. with mineral acid (BrBk-BBk), 
upon reduction yield one original component unchanged; YELLOW to ORANGE tO BROWN direct 
dyes for cotton. ‘ 

S. 13—‘‘Polychromin B.” 


951,046—Mar. 1, 1910. A. Buanxk and W. Ropionow, Germany. (Bayer.) 
Yellow to brown dye. Direct yellow with N-oxygen replaced by phenetidin. ; 


Azoxy azO DISTILBENE tetra-o-sulfo (Direct Yellow from 4-nitro TOLUENE 2-sulfo and NaOH), 
or other dye produced from 4-nitro toluene and NaOH, condensed with 4-PHENETIDENE or other 
aromatic amin by refluxing in alk. soln. for 20 hours. A yellow-brown powd., sol. in ag. 
(Y), in conc. H,SO, (BR), and pptd. on diln. as brown flakes; direct YELLOW to ORANGE to BROWN 
dyes, fast to light and oxidizing agents. 

S. 14—‘‘Diphenylchrysoin G.’”’ Note 951,047-48, S. 16—‘“‘Curcuphenine” and 951,049. 


951,047—Mar. 1, 1910. A. Bianx and W. Ropionow, Germany. (Bayer.) 
Yellow to brown dye. Direct yellow with N-oxygen replaced by amino azo benzene. 


Azo azoxy DISTILBENE tetra-o-sulfo, or other dye obtained by treating 4-nitro TOLUENE 
sulfo acid with NaOH, condensed with amino azo BENZENE sulfo or other aromatic amino azo 
comp. by refluxing 20 hours with dil. NaOH. Brown to black powd., sol. in ag. (Y-O-Br), 
sol. conc. H,SO, (VBk), pptd. on diln. (Br); direct YELLOW to ORANGE to BROWN direct dyes. 

Note 951,046. 


951,048—Mar. 1, 1910. A. BLANK and W. Roptonow, Germany. (Bayer.) 
Orange to brown dye. Direct yellow with N-oxygen replaced by dehydro thio toluidin sulfo. 


Azo azoxy DISTILBENE tetra-sulfo (from 4-nitro TOLUENE 2-sulfo and NaOH) and dehydro 
thio ToLuIpIN sulfo or other heterocyclic amin condensed by refluxing 20 hr. in dil. NaOH. 


GROUP XV.—SULFUR 247 


Brown powds., sol. in aq. (O to Br), sol. conc. H,SO, (BR), pptd. on diln. (Br); oraNcE to 
BROWN direct dyes. 
S. 16—“Curcuphenine.” Note 951,046. 


951,049—Mar. 1, 1910. A. BLankK and W. Ropionow, Germany. (Bayer.) 
Reddish-brown cotton dye. Direct yellow with N-oxygen substituted by sulfanilic azo 1- 
naphthylamin. 


Azo azoxy DISTILBENE tetra-sulfo (from 4-nitro TOLUENE 2-sulfo and NaOH) condensed with 
SULFANILIC aZ0 NAPHTHYLAMIN. Yellow brown powd., sol. in aq. (Br), sol. conc. H,SO, (V), 
pptd. on diln. (Br); red-prown direct dye. 

Note 951,046. 


Group XV.—SULFUR. 


A distinction has been made between hydrosulfite or “reducing vat” dyes and 
“sulfide vat” dyes, in which NazS acts as a solvent of the reduced dye. Both are in 
fact in the reducing vat class and many sulfur dyes, thrown out of NaeS solution 
by acid, are subsequently dyed in hydrosulfite vat. 


523,138—July 17, 1894. Raymond Vipat, France. 
Black dye. (Process only claimed.) 
QuINONE or other ortho or para dioxy benzene, heated with $, NH,Cl and NaOH in 


closed vessel at 160-210°. NH, must be freed. Treated with sulfuric acid, black dye is pptd. 
while soln. gives RED to BLUE direct dye on oxidation. Product is a BLAcK sulfide vat dye. 


5623,138—July 17, 1894. (Re. 11,659)—Apr. 5, 1808. Raymond VipaL, France. 
Black dye and process of making same, : 

QUINONE, hydroquinone, or any ortho or para dioxy benzene, heated in open or closed 
vessel to 130-210° with S and NH,, or fatty amin. Product is sol. alk. and sulfites and may 
be sulfonated, ppt. forming sBLacxk sulfide vat dye, and liquor on neutn. and oxidation a BLUE 
direct dye in neut. bath or rEp acid dye in acid bath. 


532,484—Jan. 15, 1895. Alcide F. Porrrier, France. (St. Denis.) 
Sulfur dye. (Process claimed.) p-Dioxy tetra phene trithiazine. (Green.) 

2.7- or 2.6-Dioxy NAPHTHALENE or other doubly- substituted benzene deriv., with sulfur, 
NH,Cl and Na,S heated to 175-200° in open or closed vessel. Patent employs also naphtho- 
quinones, 4-phenylene diamins, 2-diamins, naphthalene diamins, nitramins, amino-azo-benzene, 
indamins, cresylene diamins, etc. Gray or bronzy powds.; BLack sulfide vat dyes. 

See 532,503. 


532,503—Jan. 15, 1805. Raymond Vipayu and Alcide F. Porrrizr, France. (St. Denis.) 
Sulfur dye. (Process only claimed.) 

Nitroso I1-NAPHTHOL heated with S and Na,S to 190-200°. Other nitroso phenols, amino 
phenols, or nitro phenols, etc., are claimed, the latter being reduced by Na,S before sulfur is 


added to melt. Buracx sulfide vat dye. 
S. 717—“Vidal Black. Addition to 532,484. 


545,336—Aug. 27, 1895. Réne Boun, Germany. (Badische.) 
Black dye. 

1.8 or 1.5-Dinitro NAPHTHALENE boiled in aq. Na,S soln., then in strong HCl, or acetic acid. 
Ppt. contains two dyes, sol. and insol. in soda and methods for separation are given. Patent 
claims generically the mixed dyes and specifically the alk. insol. portion, which forms a blue 
black paste or black powd. with coppery luster, almost insol. NaOH, H,SO, and alc., and is a 


BLACK reducing vat dye. 
S. 740—‘“‘Fast Black B.” Note 545,337, for specific claims on alk. sol. portion. 


545,337—Aug. 27, 18905. Rene Boun, Germany. (Badische.) 


Black dye. 


1.8 or 1.5-Dinitro NAPHTHALENE stirred in aq. Na,S soln, cold, and acetic acid added to ppt. 
dye. Two products, alk. sol. and insol. are separated, the first being claimed by this patent. 


248 DIGEST OF PATENTS 


Green blue paste, or blue black powd., sol. in boiling soda (V), in conc. sulf. (G) on heating 
(B-R), insol, in alc.; a BLACK alk. or reducing vat dye. 


S. 740—‘‘Fast Black B.” Specific claims for alk. insol. portion are 1n 545,336. 


546,576—Sept. 17, 1895. Rene Boun, Germany. (Badische.) 
Black coloring-matter. (Process claimed.) 


1.8- or 1.4-Dinitro NAPHTHALENE is converted as in 545,336, by boiling in dil. Na,S then 
with excess HCl, into a dye which is largely insol. in soda, dye ““B”, which is digested at 100° 
in equal parts 23 per cent NaOH and resulting bath used for dyeing, or dried. A black powd., 
easily sol. in aq. (BV-Bk), not pptd. by alk., pptd. by acids, sol. in conc. sulf. (dull G); a 
BLACK vat dye. 


S. 741—‘“Fast Black BS.” 


560,334—May 109, 1806. Moritz Unricu, Germany. (Bayer.) 
Black dye. (Process claimed.) 


1.4- or 1.5-Dinitro 8-cHLOR NAPHTHALENE, boiled in aq. soln. with 5 parts Na,S, filtrate 
acidified and boiled. Green black powd., insol. in aq., alc., H,SO, but sol. in hot NaOH or 
Na,S; gray BLUE to BLACK vat dyes, 


561,276—June 2, 1896. Alcide F. Porrrrer, France. 
Sulfureted dye. (Process claimed.) 


Acetyl 4-PHENYLENE DIAMIN, or other diamin or corresponding azo or nitro derivs., etc., 
heated with 2 parts S to 200-250°. Alk. sulfide may be used with S. Froducts are sol. in 
aq., in alk. sulfids, sulfites, and bisulfites, insol. in acids; yELLOw to bronze YELLOW to BROWN 
reducing vat dyes. 

S. 715—‘‘Thiocatechine.’”’ Note 532,484 and 532,503. 


561,277—June 2, 18096. Alcide F. Porrrier, France. (St. Denis.) 
Sulfureted dye. (Process claimed.) 


CRESYLENE DIAMIN, nitro 4-toluidin, or other meta diamin of benzene series heated at 
200-225° in two parts Na,S. Products are sol. in aq., alks., alk. sulfide (BrR), insol. in acids; 
YELLOW to BROWN sulfide vat dyes, fast to washing and exposure. 


Near S. 710—‘‘Immedial Yellow D.” Addition to 532,503. 


594,105—Nov. 23, 1897. Henry R. Vipat, France. 
Sulfur dye. (Process claimed.) 


Resorcin, heated with NH, and S to 260° in closed vessel. Other meta dihydroxy, or amino 
oxy, diamino, sulfonated or triamino derivs. of benzene are claimed. Products are brown to 
black powds., sol. in Na,S (Br); BROWN or BLACK sulfide vat dyes. 


Near S. 717—‘‘Vidal Black Y.” 


594,106—Nov. 23, 1897. Henri R. Vina, France. 
Mixed sulfur dye. (Process claimed.) 


4-PHENYLENE DIAMIN and HYDROQUINONE, equal parts, heated in sulfur. Two colors are 
formed, one soluble in acids, the other soluble in alkalies; BLAcK acid or dull BLUE alk. vat dyes. 


594,107—Nov. 23, 1897. Henri R. Viva, France. 
Thiazin dye. (Process only claimed.) 4.4’-Dioxy thiazine, and 4-amino 4/-oxy thiazine. 


1.4-Amino PHENOL, with or without 4-PHENYLENE DIAMIN, and HYDROQUINONE heated with S. 
Brack sulfide vat dyes, (not claimed). 


Note 601,363 and 601,364. 


596,559—Jan. 4, 1898. Arthur WEINBERG, Germany. (Cassella.) 
Brown sulfureted dye. (Process claimed.) 


Dinitro crEeso, heated with 1-3 parts S and 4-6 parts Na,S to 100°. A BRown sulfide 
vat dye. 


Near S. 725—‘‘Immedial Dark Brown A.”’ 


GROUP XV.—SULFUR 249 


597,983—Jan. 25, 1808. Max H. Isier, Germany. (Badische.) 
Black substantive cotton-dyestuff. (Process claimed.) 


1.5-Dinitro ANTHRAQUINONE or other nitro, amino or sulfo anthraquinones, heated with 
Na,S and § till soluble in aq. Product is sol. in aq. (B), in conc. sulf. (GyBk), slightly sol. 
in alc. (G), insol. in acids, sol. in alk. and alk. sulfids; a spracx sulfide vat dye, fast to light, 
acids, soap, Cl. 


S. 749—“Anthraquinone Black.’’ 


601,363—Mar. 29, 1808. Henri R. Vina, France. 


Thiazin dye. Tetraphene trithiazine products with OH or NH, in para position in each 
end nucleus. 


1.4-Dioxy THIAZINE, Of 4-amino 1-oxy thiazin (or mixture of 4-amino PHENOL and 1.4-PHENY- 
LENE DIAMIN) heated with S and NH, to 170-220° in closed vessel. Para substitution products 
of thiazines, or mixtures yielding same, are claimed. Black powds., sol. in conc. sulf., in 
sulfites and hot alks.; puacKx sulfide vat dyes. (not claimed). 


Addition to 594,107. 


601,364—Mar. 29, 1808. Henry F. Vipau, France. 
Process of obtaining dyes from sulfanilie acid. 


SULFANILIC acid and 4-amino PHENOL heated at 170° (boiling temp.) for 2-3 hours. Other 
amino phenols or naphthols and analogs of sulfanilic acid are claimed. Buiue to violet BLUE 
vat dyes. 


Note 608,354 for specific claims. 


601,365—Mar. 20, 18098. Henri R. Vipat, France. 
Black dye. (Process also claimed.) 


SuULFANILIC acid, or other amino sulfo aryl derivs., 4-amino PHENOL, or other amino phenols, 
naphthols, diamins, etc., heated in strong NaOH till dissolved, sulfur added and temp. raised to 
170°. Dark poreus mass, insol. in acids, sol. in alks. (BBk), darker in air; sBLacK sulfide 
vat dyes. 


Note 608,355 for specific claims. A 


603,755—May 10, 1898. _ Robert Demutu, New York. (Bayer.) 
Brown sulfur dye. (Process also claimed.) 


CreEsoL, either crude, the separated isomers or mixtures, heated with strong NaOH and S 
to 270°. Brown black powd., insol. in aq., alk. carb., NH, alc., diff. sol. NaOH (GBr), insol. 
conc. sulf., sol. in alk. sulfids (GBr); fast Brown sulfide vat dyes. 


606,193—June 28, 1808. Robert Demutu, Germany. (Elberfeld.) 
Yellow-brown cotton-dye. (Process also claimed.) 


2.4-Dinitro TOLUENE 6-SULFO, heated with soln. of Na,S and S to 200-250°. Dark brown 
powd., easily sol. in aq. (RBr), not changed by Na,S, pptd. from soln. by acids (Br); yellow 
BROWN sulfide vat dyes, fast to alks. and light. 


Near S. 722—‘‘Auronal Black N.”’ 


608,354—Aug. 2, 1898. Henri R. Vipat, France. 
Process of making violet dyes. 


SULFANILIC acid and 1.4-PHENYLENE DIAMIN or 1.4-naphthalene diamin heated to 170-225° 
(boiling temp.) 2-3 hours. Products are sol. in acids (V), in alks. (VBk); dark viouer direct 
dyes (not claimed). 


608,355—Aug. 2, 1898. Henri R. Vipat, France. 
Brown-black sulfur dye. (Process claimed.) 


SuULFANILIC acid, or other aminobenzene sulfo acid, and 2-amino PHENOL, or other amino 
phenol or diamin, heated with sulfur to 170-200° and dye dissolved out with alkali. Dark mass, 
sol. in alks., insol. in acids; BROWN to BLACK vat dyes. 


Note 601,365. 


250 DIGEST OF PATENTS 


610,541—Sept. 13, 1898. Georg KaiscHER, Germany. (Cassella.) 
Black dye and process of making: same. 

1.3-Dinitro 4-chlor BENZENE, or the nitro amino or diamino compound condensed with 
4-amino PHENOL in alc. sol. in presence of acetates, to 4-oxy 2/.4'-dinitro DIPHENYLAMIN, which 
with Na,S and § is heated to 140-160°. A black mass, sol. in aq. (BBk), pptd. from soln. 
by acids; a blue BLACK vat dye. 

S. 724—‘‘Immedial Black.” Note 628,607 and 628,609 for sulfo derivs., 639,806 for similar 
components and process, 651,077 for chlorine deriv., and 692,174 for use of Cu in melt. 


611,112—Sept. 20, 1808. Emil E.sarsser, Germany. (Dahl.) 
Blue-black dye and process of making same. 

1.8-Dinitro NAPHTHALENE 4-sulfo soln. in cold aq. added to soln. of Na,S in® aqi=e “Dark 
powd., readily sol. in aq. (B-Bk), sol. conc. sulf. (BrBk), pptd. on diln. (Br); sLuE to blue 


BLACK (Cr and Cu) vat dyes, fast to washing and light. 
Near S. 740—‘‘Fast Black B.” 


611,610—Oct. 4, 1898. Robert DEMutH, Germany. (Elberfeld.) 
Brown cotton-dye. (Process claimed.) 
I-NAPHTHOL 4.8-disulfo, treated with Na,S and S in aq. soln. in closed vessel at 260—-270°. 


A black mass or powd., sol. in aq. (RBr), unchanged by Na,S, pptd. from soln. by acids (Br); 
red BROWN alk. vat dyes, fast to alks. and light. 


611,611—Oct. 4, 1808. Robert DEmutTH, Germany. (Elberfeld.) 
Indigo-blue cotton dye. (Process claimed.) | 


I-AMINO 8-NAPHTHOL, heated in closed vessel with Na,S, sulfur and aq. to 200-240°, melt 
extracted with aq., and soln. pptd. with NaCl, ZnCl,, etc. A black powd., insol. in aq., alk. 
carb. or HCl, largely sol. in NaOH, 40° (B), in conc. sulf. (dull VR), in hot aq. Na,S (Br), 
turning with air to (B); a BLUE alk. reducing vat dye, fast to alks. and light. 

Note 614,538. 


614,538—Nov. 22, 1808. Robert DEMutH, Germany. (Elberfeld.) 
Indigo-blue dye and process of making it. 


I-AMINO 8-NAPHTHOL 2.4-disulfo, or other disulfo deriv., heated dry with Na,S and §S to 
200-240°. Dye extracted from melt with hot aq. and pptd. by ZnCl, salt, etc. Dark powds., 
insol. in aq., alk., carb., and HCl, sol. in 40° NaOH (B), in conc. sulf. (dull VR), in dil. 
NaS (Br), turning in air to (B); BLuE reducing vat dyes, fast to alks., light. 

Note 611,611 


618,152—Jan. 24, 1899. Henri R. Vipat, France. 
Black sulfur dye. (Process claimed.) 


2.4-Dinitro PHENOL, 2.4-diamino PHENOL, the corresponding naphthols or other trisubstituted 
derivs., heated to 140° with Na,S and S. Black powds., sol. in alk. sulfide, in alks., and in 
acid bichromate solns.; BLACK sulfide vat dyes. 

S. 720—‘‘Sulfur Black.” This patent appears to duplicate 655,659. Schulz credits it to 
Priebs and Kaltwasser, 1899. 


620,428—Feb. 28, 1899. Robert Demutu, Germany. (Elberfeld.) 
Blue cotton dye. 

1-Chlor 8-NAPHTHOL 2.4-disulfo or mono sulfo, in alk. soln. with Na,S and S, or other 
poly sulfids, heated to 200-240°, melt extracted by aq., and pptd. by ZnCl, or salt, ete. Dark 
powd., insol. in aq., alk. carb., and HCl, largely sol. in 40° NaOH (B), in conc. sulf, (dull 
VR), in hot dil. NaS (Br), turning with air to (B); BLuE reducing vat dyes, fast to alk. and 
light. 


622,299—Apr. 4, 1899. Henri R. Viva, France. 
Black dye and process of making same. 

Gun corron (hexa NITRO CELLULOSE) or other nitro aromatic substance from cellulose 
material heated with Na,S and S and water to 280°. Brown sLacK to deep sack sulfide 
vat dyes. 


+e: 


_ 


GROUP. XV.—SULFUR 251 


626,897—June 13, 1890. Friedrich Fucus and Hermann GussmMAnNn, Germany. (Hochst.) 
Black sulfur dye and process of making same, 


2.4-DINITRANILIN or diamino nitrobenzene heated with Na,S and S to 150° then to 230— 
240°: Black hygroscopic powds., sol. in aq., pptd. by acids (Bk), sol. in alk. sulfide or 
caustic; BLACK sulfide vat dyes, (cold bath), fast to alks., acids, light. 


628,607—July ‘Ti, 1899. . Bernhard Prigss and Oskar KattwassEr, Germany. (Berlin.) 
Black dye. 


2-Nitro 1-chlor BENZENE 4-sulfo condensed with 4-amino PHENOL to form 4’-oxy 2-nitro 
DIPHENYLAMIN 4-sulfo, which with Na,S and S is heated to 140-150° then at 180-200°. Product 
is easily sol. in aq. (GB), in fuming sulf. (GyG-GGy), soln. pptd. by air (Bk-BGy); fast 
BLACK vat dye. 

Near S. 724—‘Immedial Black.”’ Note addition patent 628,609, original pat. by Kalischer, 
610,541 and 641,100. 


628,608—July 11, 1899. Bernhard Prigss and Oskar Ka.twassErR, Germany. (Berlin.) 
Black dye. 


4.2-Dinitro 2’.3’-carbo DIPHENYLAMIN, obtained by interaction of 2.4-dinitro chlor BENZENE 
and 4-amino sALIcyLic acid, heated in sulfur melt at 130-140°, then at 160-170°. Product is 
sol. in aq., (GB), in fuming sulf. (GyG), pptd. on diln. (BBk), pptd. by air (dull B); fast 
deep BLACK alk. vat dye. 


628,609—July 11, 1899. Bernhard Priess and Oskar Kaitrwasser, Germany. (Berlin.) 
Bluish-black dye. 


4.2-Dinitro 1-chlor BENZENE, condensed with 4-amino PHENOL 2-sulfo to form 4’-oxy 4.2- 
dinitro 3’-sulfo DIPHENYLAMIN, which is heated with Na,S and S to 140-160°. Product is sol. 
in aq. (B), in fuming sulf. (GyB), pptd. on diln..(V), pptd. by air; blue BLacxk sulfide vat dye. 

Near S. 724—‘‘Immedial Black.’”? The same as 724 except above employs sulfo deriv. in 
first component. See also original patent by Kalischer, 610,541 and 628,607. 


629,221—July 18, 1899. Henri R. Viva, France. 
Cresol-sulfur dye and process of making same. 

ANILIN diazotized and coupled with crEsoL (o or m), heated with soda and sulfur to 180° 
until anilin is distilled off, then temp. raised to 240°. Black brittle substances, sol. in aq., 
pptd. by acids, sol. in alk. sulfids; BLack (ortho deriv.) or BLUE (meta comp.) sulfide vat dyes 
that do not require oxidation on fiber. 

Note 523,138, 532,484 and 532,503. 


630,952—Aug. 15, 1809. Henri R. Vipat, France. 
Substantive sulfur dye and process of making same. 


ANILIN and RESORCIN, the disazo resorcin or dioxy naphthalene comps. or the amino or 
diamino dioxy derivs. of naphthalene (products by reduction of above) heated with Na,S and 
S at 220-280°. Black brittle mass, sol. in aq., giving VARI-COLORED dark shades as sulfide vat 
dyes. 


632,170—Aug. 29, 1899. Rene Boun, Germany. (Badische.) 
Blue dye and process of making same. 


1.2-Dinitro NAPHTHALENE, reduced by alk. bisulfite, Na,S and glucose, or other, then heated 
with Na,S and S to 90-100°. Buiue reducing sulfide vat dyes. 

S. 743—‘‘Kryogen Brown A.” Note 674,137 for similar patent and apparent duplication. 
Addition to 609,327. 


635,168—Oct. 17, 1899. R. KircHHoFF and E. HaussMann, Germany. (Berlin.) 
Black sulfur dye. 


2.4-Dinitro 4/-oxy DIPHENYLAMIN, 1 mol., or derivs. and 1 mol. 4-amino PHENOL, heated 

with Na,S and S to 110-160°. 4-Phenylene diamin, or nitro derivs. may be used. Products 
are sol. in aq. (GB), with NaOH bluer, pptd. by acids, air or CO, (BrBk), sol. conc. sulf. 
(dull BrG), in fuming sulf. (BBk); green sLack sulfide vat dyes, that do not require oxidation 
on fiber. Patent does not state whether product is a single compound, or mixture of sulfur 
dyes produced from separate components. 

Note 610,541 and 625,717. 

17 


252 DIGEST OF PATENTS 


635,169—Oct. 10, 1899. R. Krrcuuorr and E. Haussmann, Germany. (Berlin.) 
Black sulphutur dye. 


2.4-Dinitro 4’-oxy DIPHENYLAMIN and equimolecular proportion of 3-PHENYLENE DIAMIN 
heated in Na,S and S at 120-125° then at 150-160°. Other components cla‘med. Brack sul- 
fide vat dyes. 


Near S. 724—‘‘Immedial Black.” Note 610,541 and 625,717, 561,277 and 594,105. 


636,066—Oct. 31, 1899. Christopher Ris, Switzerland. (Geigy.) 
Black-cotton dye. 


4-Amino PHENOL or deriv., mixed with ACETANILID or other acetyl aryl comp., with or 
without diluent such as GLYCERIN, etc., heated with sulfur at 210-230°,, till H,S ceases to 
evolve. Black powds., easily sol. in aq. (GBr), in conc. sulf. (GBk), insol. alc., ether, C,H,; 
BLACK sulfide vat dyes. 


639,806—Dec. 26, 1899. W. H. Craus, A. REE and Leon Marcuiewsk1, England. 
Black sulfur dye. (Process only claimed.) 


2/-Oxy 2.4-dinitro DIPHENYLAMIN, heated with Na,S and S to 140-160°. A BLAcK reducing 
sulfide vat dye, fast to light, acids, alks. 


Near S. 724—‘‘Immedial Black.”” Use of ortho hydroxy compound instead of para, claimed 
as new, see 610,541. 


640,559—Jan. 2, 1900. Otto Hansmann, Germany. (Berlin.) 
Brown sulfur dye. 


4-Nitro 1-chlor BENZENE 2-sulfo, condensed with 3-TOLUYLENE DIAMIN by refluxing with 
aq. in presence of CaCO, until CO, ceases to evolve, filt., filtrate pptd. by acid and dried 
product heated at 180-200° with Na,S and S. A brown black powd., sol. in aq. (Br), un- 
changed by NaOH, pptd. by acids (Br), sol. conc. sulf. (dull VR), pptd. on diln. (Br), diff. 
sol. alc. (Br); a Brown sulfide vat dye turning to bronze when after treated with CaSO, and 
KOCr0.. 


Near 737—‘‘Cotton Brown.” 


641,587—Jan. 16, 1900. Arthur G. Green and A. Mryenserc, England. 
Process of making black sulfur dye. 


4-PHENYLENE DIAMIN mixed in dil. HCI soln. with 1 mol. anrnin HCl, about 5 parts Na,S,0, 
dissolved in this soln., then Na,Cr,O, and excess sulf. acid added, keeping temp. below 5°, 
finally soln. is boiled. Para amino phenol and other paradiamines and bases of benzene series 
are claimed. : 


Note 641,588 and 89 for product pat. and homologous dyes. 


641,58S—Jan. 16, 1900. Arthur G. Green and Alex. MEYENBERG, England. 
Blaek sulfur dye. 


oS oe ae 


4-PHENYLENE DIAMIN mixed in dil. HCl soln. with anizin HCl, nearly 5 parts cryst. 
Na,S,O, added, then sod. bichromate and excess sulf. acid, with temp. kept below 5°, and soln. 
finally boiled. Other para diamines and other bases of benzene series are claimed. Brack 
reducing sulfide vat dyes, fast to acids, alks., soap, light, and air, and may be developed by 
copper salt and bichromate. 

This is product patent for process 641,587. Note also 641,589. 


641,589—Jan. 16, 1900. Arthur G. Green and Alex. Mryenserc, England. 
Black sulfur dye. 


i 
’ 
a 
* 
% 


4-TOLUYLENE DIAMIN mixed in HCI soln. with 1 mol. anizin HCI or 2-toluidin HCl, nearly 
5 parts Na,S,O, dissolved in bath, then bichromate and excess. sulf. acid added while temp. 
is kept below 5°. Later more sulf. acid is added and soln. boiled. Black powd., insol. in 
aq., acids, alk. carbonates, sol. in alk. sulfids and sulf. acid (BBk); siack reducing sulfide vat 
dyes, fast to soap, light, air, and may be developed by chromate or copper salt. 


Addition to 641,588. 


GROUP XV.—SULFUR 253 


641,953—Jan. 23, 1900. Arthur G. Green and Alex. Mryenserc, England. 
Process of making fast brown dyes. 

4-TOLUYLENE DIAMIN HCl, 2-PHENYLENE DIAMIN HCl, or other ortho or para diamino ben- 
zene deriv. in aq. soln. with Na,S,O, to which Na,Cr,O, and H,SO, in excess are added, mix- 
ture allowed to stand at 20-25°, then more sulfuric and bichromate added and soln. boiled. 


For product see 641,954. 


641,954—Jan. 23, 1900. Arthur G. Green and A. Mryvenserc, England. 
Fast brown dye. 

3-TOLUYLENE DIAMIN HCl, oxidized in aq. soln. by sulfuric and bichromate in presence of 
Na,S,0,. Brown black powd., insol. in aq., acids, diff. sol. in alk. carb., easily sol in Na,S 
(Br) and in conc. sulf. (GBk), may be reduced to leuco form and reoxidized; sprown reducing 
sulfide vat dye, fast to acids, alks., soap, air, light. 


Near S. 711—‘‘Immedial Orange B.”’ For process pat. see 641,953. 


642,256—Jan. 30, 1900. Bernhard Prigss and Oskar Kattwasser, Germany. (Berlin.) 
Blue sulfur dye. 

2.4-Dinitro 4’-oxy DIPHENYLAMIN sulfo, carboxy, or other derivs., heated in sulfur melt by 
usual process, product refluxed with to parts alc., and residue dried in air. Products after 
alc. treatment differ from original comps. in physical, chemical and tinctorial properties. 
Dark brown powd., sol. in aq. (VB), unchanged by NaOH, pptd. by excess NaOH (BBk), 
aq. soln. pptd. by acids (RV), sol. in conc. sulf. (VB), insol. in alc.; dark BLUE vat dye. 


Deriv. of S. 724—Immedial Black F. P.” or 737, “Cotton Brown.” 


644,959—Mar. 6, 1900. Julius Ase,, Germany. (Badische.) 
Green-black dye. 

2-AMINO PHENOL 4-sulfo acid condensed with 1.2-dinitro 4-chlor BENZENE, to form 2-hydroxy 
2'.4’-dinitro DIPHENYLAMIN 5-Sulfo, which is heated with Na,S, sulfur and some water to 
160-170°. Product is sol. in aq. (G), pptd. by HCl or NH,Cl (BrBk); green sBiack sulfide 
vat dye, fast to light, acids, alks., soap, unchanged by after treatment with copper salt or 
chromate. 

Near S. 738—‘“Cotton Black.” 


645,738—Mar. 20, 1900. Christopher Ris, Switzerland. (Geigy.) 
Black sulfur dye. Probably 5-mercapto p-imino quinone N-(4”-oxy phenyl) 2-(2’.5’.- 

dimercapto p-imino quinone). 

4-Amino PHENOL, or other para amino deriv., heated in sulfur melt with oxy azo BENZENE 
or other oxy azo comp. to 200-220°, with or without cGLiycErIN. Black powd., easily sol. in 
aq. (BGBr), pptd. by acids (Br), turned by bichromate to (Bk), diff. sol. alc., insol. ether and 
C,H,, sol. in conc. sulf. (dark G); blue siacx reducing sulfide vat dyes, turned deeper and 
faster black by oxidation by chromates, CuS,, FeCl,, H,0,, etc. 


646,873—Apr. 3, 1900. Alcide F. Porrriger, France. 
Process of making sulfur dyes. 

PueEno., carefully mixed with 2 parts SO,Cl,, heated to 150-160°, 0.5 part 4-PHENYLENE 
DIAMIN added and temp. raised to 200°. For use in dyeing, product is melted in Na,S. Other 
phenols, amines, sulfo acids, or combinations of these are claimed. Black powds., sol. in 
Na,S, pptd. by acids, salt, and conc. alks.; Back sulfide vat dyes, deeper when oxidized by 
air, chromates, etc., and giving insol. combinations with metallic oxides. 


647,846—Aug. 17, 1900. Richard Kircuorr and Emil Haussmann, Germany. (Berlin.) 
Black sulfur dye. 


2.4-Dinitro 4’-oxy DIPHENYLAMIN and 2.4-dinitro PHENOL in equimolecular mixture, heated 
in sulfur melt to 140-160° till dry, or soln. of melt may be pptd. by acids. Product is sol. 
in aq. (GBk), pptd. by salt, acids, also CO, (BrB), pptd. by hot NaOH, (Bk), sol. conc. sulf. 
(BrG), in fuming sulf. (BBk), pptd. on diln. (GBk); deep BLack sulfide vat dyes. 


Near S. 725—‘‘Immedial Dark Brown A.” Note 647,847. 


254 DIGEST OF PATENTS 


647,847—Apr. 17, 1900. Richard Kircuorr and Emil Hausmann, Germany. (Berlin.) 
Black sulfur dye. 


2.4-Dinitro 4’/-oxy DIPHENYLAMINE and PICRAMIC acid or picric acid in equimolecular parts, 
heated in sulfur melt to 140°. Products sol. in aq. (BBk), pptd. by salt, acids or CO,(GBk), 
bluer with NaOH, sol in conc. sulf. (B), in fuming sulf. (dark V), pptd. on diln. (dark V), 
can be reduced to leuco form and reoxidized; deep BLAcK reducing vat dye. Dye is compound 
one and is not a mixture of two sulfur dyes from components. 

Addition to 647,846. 


648,597—May 1, 1900. Alcide F. Porrrier, France. 
Process of making sulfur dyes. (Product claimed.) 


4-Amino PHENOL and I-NAPHTHOL, or nitroso deriv., heated to 200° with sulfur, then 
Na,S added and heated to 180-200°. 2-Nitranilin, 1.2-phenylene diamin, 1.3.4- or 1.2.6- 
triamino benzene, or other amino, azo, nitro aryl derivs. or other amino phenolic comps., may 
be used. Brown RED, BROWN, or BLACK sulfide vat dyes, fast to alks. 


648,753—May 1, 1900. Paul Junius, Germany. (Badische.) 
Blue-black sulfur dye. 


4'.4”-Dioxy 3'.3”-dicarboxy diphenyl 4.6-dinitro 3-PHENYLENE DIAMIN, heated in iron vessel 
at 140° with 2 parts sulfur, 6 parts cryst. Na,S, and a little aq. until dry. Product is sol. 
in aq. (BG), pptd. by acids (Br), reduced by alks., (BG); a blue sack sulfide vat dye not 
changed by after treatment with Cr or Cu, fast to soap, light, and acids. 

Note 648,754 and 55. 


648,754—May 1, 1900. Paul Jutius, Germany. (Badische.) 
Green-black sulfur dye. 

4'-.4”-Dioxy 3'.3”-disulfo diphenyl 4.6-dinitro 3-PHENYLENE DIAMIN, heated in an iron 
vessel at 140° with 2 parts sulfur, 6 parts Na,5, and a little aq., until dry. Product is sol. 
in aq. (G), pptd. by HCI (Br), resol. in NaOH (G); a green sBiack sulfide vat dye unchanged 
by Cr. or Cu. treatment, fast to soap, light, acids. 

Addition to 648,753. 


648,755—May 1, 1900. Paul Junius, Germany. (Badische.) 
Black sulfur dye. 


4’.4”-Dioxy diphenyl 4.6-dinitro 3-PHENYLENE DIAMIN, heated to 140° with 2 parts sulfur, 
6 parts Na,S and a little aq. till dry. Product is sol. in aq. (B), pptd. by HCl (Br), resol. in 
alk. (B); a BLAck sulfide vat dye, unchanged by Cr. or Cu. treatment. 

Addition to 648,753. 


649,218—May 8, 1900. Carl ScuiEussNER, Germany. (Hochst.) 
Process of making black naphthazarin sulfur dye. (Product claimed.) 


Intermediate product in mfr. of NAPHTHAZARIN from 1.5 or 1.8-dinitro naphthalene, heated 
with Na,S and §$, with or without ZnCl, to 150~-180°. Blue gray powd., sol. in aq. or NH,, 
caustic or alk. carbonate (B), pptd. by acids, diff. sol. in alc.; a BLAcK sulfide vat dye changing 
from blue to black with Cu on fiber. 

S. 745—‘‘Melanogen Blue.” Note 561,122 for use of naphthazarin and 667,486 for 
different method of using 1.5 or 1.8 dinitro naphthalene. h 


650,292—May 22, 1900. Julius Apr, and Fritz Katxow, Germany. (Badische.) 
Brown sulfur dye. 

4-Amino PHENOL 2-sulfo, nitrated and condensed with 2.4-dinitro chlor BENZENE to form 4- 
hydroxy 3-nitro 5-sulfo 2/.4’-dinitro DIPHENYLAMIN which is heated in sulfur melt to 140°. 


Dark powd. sol. in aq. (VBr), pptd. by acids (Br); dark Brown sulfide vat dye, darkened by Cu 
treatment. 


9 Lal Ab eal aida ca 


650,293—May 22, 1900. Julius ABEL and Fritz Ka,xow, Germany. (Badische.) q 
Black sulfur dye. 


4-Amino PHENOL, its sulfo acid or other deriv. condensed with 2.4-dinitro chlor BEN- 
ZENE, 2 mols., to a tetranitro diphenyl amino phenol ether, then heated in sulfur melt to 140°. 


GROUP XV.—SULFUR 255 


Products are sol. in aq. (BG), pptd. by salt (BG); green siacxk sulfide vat dyes, fast to alks., 
acids, soap, bluer when treated with bichrom and sulf. acid, then fast to soap, Cl and SO,. 
Near S. 724.—‘‘Immedial Black.” 


650,826—May 22, 1900.° _ Paul Junius and Friedrich Reusotp, Germany. (Badische.) 
Brown-black sulfur dye. 

4.6-Dinitro 1.3-dichlor BENZENE, 2-amino PHENOL HCl and 4-amino pHENor HCl condensed 
to form 4.6-dinitro 2’-4”-diphenol 3-PHENYLENEDIAMIN, then heated in sulfur melt to 140-160°. 
Product is sol. in aq. (V), pptd. by HCl (dull V); a brown srack sulfide vat dye, turned 
browner with bichromate or H,O, treatment. 


650,327—May 22, 1900. Paul Juuius and Friedrich Reusoip, Germany. (Badische.) 
Black sulfur dye. 
2.4-Dinitro 5-amino 4’-oxy DIPHENYLAMIN heated in 6 parts Na,S, and 1.67 parts sulfur at 


140-150°. Product is sol. in aq. (GB), pptd. by HCl (YBr); deep sBLack sulfide vat dye not 
changed by Cu, Cr, or H,O,. 


651,077—June 5, 1900. Oskar KattwassEr, Germany. (Berlin.) 
Green-black sulfur dye. 

2-Amino 4-chlor PHENOL condensed with 2.4-dinitro chlor BENZENE to form 2.4-dinitro 5/- 
chlor 2-oxy DIPHENYLAMIN, which is heated in sulfur melt to 140-150°. Product is insol. in 
alc., sol. in aq. (BG), turning with NaOH (BrV), pptd. from soln. by salt (GBk) by acids or 
air (BrBk), sol. in conc. sulf. (dull G), on heating, (BkV), sol. fuming sulf. (BkG), pptd. on 
diln. (BkV), can be reduced to leuco dye and reoxidized; a green BLack sulfide vat dye. 

Near S. 724—‘“Immedial Black.”” Same components as 724, with chlorine atom in meta 
position, and hydroxyl group in ortho position, see 610,541. 


651,122—June 5, 1900. Carl ScHLEUSSNER, Germany. (Hoéchst.) 
Naphthazarin sulfur dye and process of making same. 

NAPHTHAZARIN heated in sulfur melt with ZnCl, to 160-170°. Blue gray powd., easily sol. 
in aq. (B), diluted soln. (RV), pptd. by acids and resol. in alk. or alk. carbonate (RV-B); red 
VIOLET to fast deep BLACK when treated with Cu. 

Addition to 649,218. 


653,277—July 10, 1900. Arthur AsHwortH and Joshua Bircer, England. 
Process of making black sulfur dye. 
2-Nitroso NAPHTHOL, or other nitroso phenol or naphthol, condensed with PHENOL in strong 
sulf. acid, made alk. and heated with sulfur to 180°. Alk. salts of product are sol. in aq., insol. 
in ether, slightly sol. in hot alc., and the free color acid is insol. in aq. Dye not claimed. 
Process for 653,278. 


653,278—July 10, 1900. Arthur AsHwortH and Joshua Burcer, England. 
Brown sulfur dye. 
4-Nitroso PHENOL, 2-nitrosonaphthol, or other, condensed with PHENOL, then heated with 
sulfur to 180°. Alk. salts of products are sol. in aq., insol. in ether, slightly sol. hot alc., free 
color acid is insol. in aq.; green BLACK to BROWN alk. vat dyes, deeper in shade when oxidized. 
Near S. 717—‘“‘Vidal Black I.” For process see 653,277. 


653,670—July 17, 1900. Ernst GorseL, Germany. (Elberfeld.) 
Olive cotton-dye and process of making same. 

2.4-Dinitro chlor BENZENE and monomethyl or unsym. dimethyl diamins, condensed to pro- 
duce dimethyl 4’-amino 2.4-dinitro DIPHENYLAMIN, and product heated in Na,S and S melt in 
three stages, 90—-100°, then 150-160°, and finally 280-290°. Dark powds., sol. in aq., in 10 per 
cent NH, (GBr); green srown sulfide vat dyes. 

Near S, 728—“Immedial Pure Blue.” 


655,659—Aug. 7, 1900. Bernhard Prizss and Oskar Kattwassrer, Germany. (Berlin.) 
Black sulfur dye. 


2.4-Dinitro PHENOL, boiled in aq. with Na,S and S. Black powd., insol. in aq., sol. in Na,S 
soln. which with NaOH is bluer, pptd. by acids and air, insol. in alc., sol. in hot conc. sulf. 


256 DIGEST OF PATENTS 


(dark B), pptd. on diln. (GBk), may be reduced to leucd form and reoxidized; a BLacK sulfide 
vat dye. 


S. 720—‘‘Sulfur Black textra.” Note 618,152, which apparently gives the same product. 
Process is different but no process claims are made. 


656,631—Aug. 28, 1900. Robert Demutu, Germany. (Elberfeld.) 
Violet cotton-dye and process of making same. 


Nitroso 1.8-dioxy NAPHTHALENE 2.4-disulfo, or other, reduced to amino oxy compound, then 
fused with Na,S, S, and ZnCl, at 200-240°. Black powd., largely sol. in aq., in hot NaOH and 
Na,CO,, in conc. sulf. (RV), pptd. from soln. by acids; blue vioLET sulfide vat dyes, fast to alks. 
and light. 


657,768—Sept. 11, 1900. Hermann GussmMann, Germany. (Héchst.) 
Blue cotton sulphur dye and process of making same. 


4-Nitro chlor BENZENE 2-sulfo condensed with 4-amino PHENOL, reduced to amino comp., 
fused in alkali to 2.4’-dioxy 4-amino DIPHENYLAMIN, heated in sulfur melt to 160—200°, and 
finally oxidized. Dark brown powd., of coppery luster, sol. in aq. (B), pptd. by acids as free 
dye acid which is insol. in aq. but sol. in alks., sol. in conc. sulf. (dull BG), on diln. (B), and 
pptd.; a BLUE acid mordant dye. 


Note 657,769. 


657,769—Sept. 11, 1900. Hermann GussMann, Germany. (Hochst.) 
Blue cotton sulphur dye and process of making same. 


2.4'-Dioxy 4-amino DIPHENYLAMIN, derived from 4’-oxy 4-amino diphenylamin 2-sulfo by alk. 
fusion, heated in sulfur melt to 160-180°, dissolved and oxidized by air. Dark powd. of cop- 
pery luster, soi. in aq. (B), pptd. by acids (B), sol. in conc. sulf. (BG); a BLUE acid mordant dye. 


Addition to 657,768. 


658,055—Sept. 18, 1900. Julius Ape, and Fritz KarKow, Germany. (Badische.) 
Brown cotton dye and process of making same. (Process not claimed.) 


1.4-Dichlor 2.6-dinitro BENZENE obtained by nitrating 1.4-dichlor 2-nitro BENZENE, condensed 
with 4-amino PHENOL, or other, to form DIPHENYLAMIN deriv., then heated in sulfur melt to 
140-150°. Product is BRowN sulfide-vat dye, fast to steam, soap, acids, SO,, and Cl., fastness 
increased by Cu. 


658,286—Sept. 18, 1900. Nikolaus Schwan and Wilhelm ZrpEL, Germany. (Hochst.) 
Brown sulfur dye and process of making same. 


1.3.8-Trinitro NAPHTHALENE, or deriv., is dissolved in aq. soln. of Na,S and S and evap- 
orated to dryness. Brown black products sol. in aq., pptd. by acids; Brown sulfide vat dyes. 


Near S. 745—‘“‘Melanogen Blue.” 


660,058—Oct. 16, 1900. Meinhard Horrman and Georg KariscHEer, Germany. (Cassella.) 
Brown sulfur dye. (Process claimed.) 

2.4-Dinitro 4’-oxy DIPHENYLAMIN, or other, from 2.4-dinitro chlor BENZENE and 4-amino 
PHENOL, boiled in alk. soln., then heated with Na,S and §, or other, to 160°. Dark brown powd., 


sol. in dil. alk., and alk. sulfids, pptd. by acids; deep BRowN sulfide vat dye, fast to washing, acids, 
oxidizing agents, faster and yellower when chromed. 


S. 725—“‘Immedial Dark Brown A.’ Note 665,726 for different process applied to sameé 
material, 


660,067—Oct. 16, 1900. Arthur WEINBERG, Germany. (Cassella.) 
Brown sulfur dye and process of making same. ? 

s-Amino 2-crESOL, (OH = 1) condensed with 2.4-dinitro chlor BENZENE to form 2.4-dinitro- a 
phenyl oxy TOLYL amin, nitrated to tetra nitro product, then heated in sulfur melt to 120°. 
Black lumps or powd., sol. in aq. (dark Br), pptd. by acids; a BROwN sulfide vat dye that may — 
be diazotized and coupled on fiber, or treated with Cu or chromate to give yellower hue. 


Near S. 725—‘“‘Immedial Dark Brown A,” part 2. Note 660,058. 


GROUP XV.—SULFUR ac. 


660,770—Oct. 30, 1900. Hermann GussmMann, Germany. (Hochst.) 
Blue sulfur dye. (Process claimed.) 


4’-Amino 4-0Xy DIPHENYLAMIN 3-carbo, from sulfo acid of same, or nitro deriv., heated in 
sulfur melt to 160-200°. Dark powd. of metallic luster, diff. sol. aq., sol. sulf. (B), converted 
to leuco comp. on reduction; a BLUE reducing sulfide vat dye. 


661,438—Nov. 6, 10900. Rene Boun, Germany. (Badische.) 
Black dye and process of making same. 


1.8-Dinitro NAPHTHALENE dissolved at 130° in 10 to 20 parts 96 per cent sulfuric, H,S passed 
through or Sb,S, added. The accompanying naphthazarin is removed from pptd. dye by alum 
soln. If reaction be continued till all naphthazarin is converted, the color is less suited for 
dyeing. Dye paste is heated at 95° with bisulfite to give soluble comp. Product is diff. sol. in 
aq. (dull BV), sol. in fuming and conc. sulf. (23 per cent SO,) (dull RV); fast Biacx acid 
mordant dye, adapted to printing. ; 
S. 740—“Fast Black B.’ Patent claims product “Superior to that obtained with naphth- 
azarin.” 


661,907—Nov. 13, 1900. Karl Exper and Ignaz Rosenperc, Germany. (Kalle.) 
Brown sulfur dye and process of making same. 


2.4-Dinitro chlor BENZENE condensed with PyRIDIN by heating to 70-80° in aq. (or by heat- 
ing dry then dissolving in water). Soln. is made alk., warmed to 80-90°, and separated ppt. 
heated in sulfur melt to 120-280°. Product is sol. in aq. (YBr), less’sol. in alc. (GY), sol. in 
conc. sulf. (YBr), pptd. from aq. soln. by HCl or salt (Br); a yellow BrRowwn sulfide vat dye, 
fast to washing, acid, alk., and light. 


665,547—Jan. 8, 1001. Alcide F. Porrrier, France. 
Black substantive sulfur dye and process of making same. 


4-PHENYLENE DIAMIN, or 4-amino phenol, oxidized with 1-NAPHTHOL, or other aryl oxy 
comp., to form INDOPHENOLS, or indoanilines, not indamins, (must contain at least one OH 
group) then fused at 200° with sulfur, Na,S added and again heated to 200°. Products are sol. 
in aq., and are BLACK sulfide vat dyes, improved by oxidation on fiber with bichromate. 

S. 730—‘‘Pyrogen Black.”’ 


665,726—Jan. 8, 1901. Albert BertscHMANN, Switzerland. (Basle.) 
Sulfurized indophenol dye and process of making same. 


2.4-Dinitro 4/-oxy DIPHENYLAMIN indophenols, or other para oxy derivs., and sodium tetra- 
sulfide in alc. soln., heated to 145° with or without NH, NaOH, anilin, sulfanilic acid, or other 
amin. ‘Two dyes are formed for which a method of separation is given. Main product is a 
deep blue cryst. powd., with coppery luster, sol. in alk. sulfide (VB); violet spLuE to dark BLUE 
sulfide vat dyes, becoming more violet on treatment with oxidizing agent. 

S. 726—‘“‘Pyrogen Direct Blue.” Note 610,541 for other part of product, and 660,058 for 
use of same material by different process. 


667,486—Feb. 5, 1001. Rene Boun, Germany. (Badische.) 
Blue sulfur dye and process of making same. 


1.5-Dinitro NAPHTHALENE dissolved in 20 parts 96 per cent sulf. acid at 130° through which 
H,S is passed for 8-10 hours. Or H,S may be passed into a NAPHTHAZARIN melt at 130°. A 
blue black powd., sol. in hot aq. (GB), not changed by NaOH, or Na,CO,, sol. in dil. NaOH 
(GB), in conc. sulf. (Br), in C,H,NO, (BV), reduced with SnCl, and HCl gives brown yellow 
leuco dye; a BLUE sulfide vat or GREEN acid mordant (Cr) dye. : 

Possibly S. 745—‘“‘Melanogen Blue.” Note 649,218 for different process using same material. 


667,689—Feb. 12, 1901. Karl Evze, and Ignaz RosENBERG, Germany. (Kalle.) 
Process of making black substantive sulfur dye. 


Dinitro 2-chlor BENzoIc acid and 4-amino PHENOL, or other chlor ortho carboxy derivs., con- 
densed to form 4-oxy dinitro DIPHENYLAMIN 2-carbo, the carbo group being in ortho position to 
imino or hydroxy group, then heated in sulfur melt to 140-150°. Black powds., sol. in aq. 
(GBk), diff. sol. alc. (GB), changed to (BBk) by NaOH, soln. pptd. by HCl (Bk), sol. conc. 
sulf. (GB), pptd. on diln. (Bk); fast BLack alk. sulfide vat dye, made faster by treating with 
metallic salts. 

S. 724—“‘Immedial Black” carbo acid. 


258 DIGEST OF PATENTS 


671,908—Aug. 9, 1901. Hermann GussMANN, Germany. (H6chst.) 
Black sulfur dye. (Process claimed.) 


4-Nitro chlor BENZENE 2-sulfo and 4-amino crESOoL condensed to 4-oxy 3-methyl 4’-amino 
2/-sulfo DIPHENYLAMIN, then reduced and heated in sulfur melt to 180—240.° Dark porous mass, 
sol. in aq. (GBr), turning with air to (VB-GB); a sBiack sulfide vat dye. 


673,388—May 7, 1901. Robert DemutH, Germany. (Elberfeld.) 
Blue cotton dye and process of making same. 


I-AMINO 8-NAPHTHOL 2.4-disulfo, mono sulfo or other disulfo derivs. in alk. soln. with zinc, 
ZnCl,, or other zinc comp., heated in sulfur melt to 200-240°. Black powds., sol. in aq. (B), in 
hot NaOH or NH,OH (B), in conc. sulf. (dull VR), pptd. from soln. by acids; Brug sulfide vat 
dyes fast to alks. and light. 

Note 614,538. 


674,137—May 14, 1901. Gustav Linx, Germany. (Hochst.) 
Brown dye and process of making same. 


1.8-Dinitro NAPHTHALENE heated in Na,S to 160-180°. A brown mass, sol. in aq. (dark Br), 
pptd. by acids, sol. in NaOH, alk. carb., NH,OH and alk. sulfids; a Brown sulfide vat dye. 

Near S. 743—‘‘Kryogen Brown A.” Note 609,327 and 632,170 for similar process and 
material. 


675,585—June 4, 1901. Melchior B6nicER, Switzerland. (Sandoz.) 
Black sulfur dye and process of making same. 


1-Chlor 4.8-dinitro NAPHTHALENE or other mono or dinitro or nitro sulfo deriv., condensed 
with 4-amino PHENOL, or same with sulfo deriv. in ortho position to OH, to form 4’-oxy phenyl 
4.8-dinitro I-NAPHTHYLAMIN which is heated in sulfur melt to 130-135°. Black powds., sol. in 
alk. sulfids (Bk), in conc. sulf. (BBk); blue BLacK sulfide vat dye, changed by oxidizing agents 
to dark BLUE (CrO,), fast to alks., acids. 

A nitro group in the benzene nucleus would change color from black to brown. 


679,199—July 23, 1901. Re. 11,973—Mar. 4, 1902. Julius AsgeLt, Germany. (Badische.) 
Blue sulfur dye and process of making same. 


Dimethyl 4-PHENYLENE DIAMIN thio sulfo or analogous comps., and PHENOL or derivs., con- 
densed by oxidation with bichromate in acetic soln. to form dimethyl amino INDOPHENOL thio 
sulfo which is heated to 125° in sulfur melt. Products are insol. in aq., HCl or Na,CO,, may be 
reduced to leuco form; BLUE reducing sulfide vat dyes. 

S. 729—“‘Kryogen Pure Blue R.” Note 1,083,110 for further use of product. 


681,689—Sept. 3, 1901. Wilhelm Epstein and Emil RosEnrtHAL, Germany. 
Brown sulfur dye and process of making same. 


BENZIDIN or derivs. nitrated to dinitro deriv., heated in sulfur melt at 260-265°. Product 
is sol. in aq., pptd. by acids; yellow Brown to brown BLACK reducing sulfide vat dye, fast to 
soap, acids, alks., deepened on fiber by oxidation with Cu, CrO,, etc. 

This compound-2.2’-dinitro-4.4’/-diamino diphenyl is termed in patent the meta dinitro deriv. 
of benzidin, counting from amino groups as 1.1’; not from common bond between phenyl 
groups. 


687,072—Nov. 19, 1901. Max Scuumann, Germany. (Badische.) 
Brown sulfur dye and process of making same. 


ACETANILID, nitrated to 2.4-dinitro acetanilid and heated in sulfur melt to 200—-240°. Prod- 
uct is sol. in aq. (Br), pptd. by acid (Br), sol. in conc. sulf. (Br), in alc. (Y); a BRowN 
sulfide vat dye, slightly yellower when chromed, fast to washing, acids, light. 

Near S. 715—‘‘Thiocatechine.” 


687,581—Nov. 26, 1901. Heinrich Srrpet, Austria Hungary. (Kalle.) 
Brown sulfur dye. 


Waste LYE from sulfite cellulose process, neut., conc., freed from Ca or not, and heated 
in sulfur melt to 120-180°. Black powd., sol. in aq., or conc. sulf. (Br), pptd. on diln. (Br), 
pptd. from soln. by acids, not changed by alks, insol. in alc.; a Brown sulfide vat dye the fast- 
ness of which is increased by after treatment with Cr, Cu or Fe salts. 

S. 708—‘‘Sulfanilin Brown 4-B.” 


GROUP XV.—SULFUR 259 


688,646—Dec. 10, 1901. Paul Jutius, Germany. (Badische.) 
Black sulfur dye and process of producing same. 

3.5-Dinitro 1,2.4-trichlor BENZENE condensed with 2 mols. 4-amino PHENOL to form 2.4-di- 
nitro 6-chlor 4’.4”-dihydroxy diphenyl 3-PHENYLENEDIAMIN by warming in alc. soln. in presence 
of sod. acetate then heated in sulfur melt to 140-180°. Product is sol. in dil. NaOH (V), 
slightly sol. in conc. sulf. (G), aq. soln. with Na,O, (dull RV); Biack sulfide vat dye, greener 
when chromed. (CrO,). 


Note 648,755, which is same product without halogen. 


688,885—Dec. 17, 1901. C. Ris, Switzerland. (Geigy.) 
Brown sulfur dye and process of making same. 

3-TOLUYLENE DIAMIN, 2 mols., and 1 mol. PHTHALIC anhyd., are melted together at 120-200° 
till aq. ceases to evolve, then heated in sulfur melt at 270-300.° Other diamins or nitro comps. 
which produce diamins upon reduction and other dicarboxylic acids may be used. Dark powds., 
sol. in aq. (OBr), in conc. sulf. (Y-OBr), in alc. (Y-O), pptd. from soln. by acids (Br), sol. in 
alk. carbonates (OBr), can be reduced to leuco form, insol. in ether and C,H,; orange BROWN 
reducing sulfide vat dye, oxidized on fiber to yellow Brown, fast to light, alks., acids and soap. 


688,999—Dec. 17, 1901. Bernard Hrymann, Germany. (Elberfeld.) 
Process of dyeing on the fiber. Producing new dyes by alkylation or alphylation of 
sulfur dyes on fiber. 

Fiber dyed with 10 per cent sulfur dye obtained from 2.4-dinitro 4/-oxy DIPHENYLAMIN as 
in 610,541, is rinsed and passed a) into bath containing 5 per cent PHENYL dimethyl ammonium 
chloride and 10 per cent NaOH (40°) at 80° or b) bath of 3 per cent chlor ACETAMID at 90°, 
with addition of 2 per cent cryst. Na,S. Other sulfur dyes and other alkyl or alphylating agents 
are claimed. Products are fast green BLUE or violet BLUE developed dyes. 


690,271—Dec. 31, 1901. Richd, O. Fr. Hatter, Germany. (Badische.) 
Brown sulfur dye and process of making same. 

sym-Hexa nitro DIPHENYLAMIN added to 5 parts Na,S at 45-50°, then 2 parts sulfur added 
and melt heated to 140°. Product is sol. in aq. (Br), pptd. by NH,Cl (Br), sol. in conc. sulf. 
(YBr); a Brown sulfide vat dye, deepened by chrome alum, and can be developed on fiber by 
diazo comps. or diazotized and developed with 2-naphthol, etc. 


692,174—Jan. 28, 1902. Julius Aspet and Fritz Kautxow, Germany. (Badische.) 
Black sulfur dye and process of making same. 

4’-Hydroxy 2.4-dinitro DIPHENYLAMIN, heated with copper sulfate, or other salt, in sulfur 
melt to 220°. Product is almost insol. in alc.; a deep siack sulfide vat dye, less green with 
CuSO,, dull blue Brack, not blue, with H,O,, fast to washing without after treatment with 
chromate. 7 

Near 724—“Immedial Black.’’ Note 610,541, etc., for similar process without use of copper 
or its salts. 


693,632—Feb. 18, 1902.’ Arthur WEINBERG and Richard Herz, Germany. (Cassella.) 
Blue sulfur dye and process of making same. 

Dimethyl 4-amino 4’-oxy DIPHENYLAMIN, is heated in sulfur melt to 115°, dissolved, pptd. 
by acids, redissolved and oxidized. Dark blue bronzy powds., sol. conc. sulf. (B), in caustic 
or alk. sulfids; a BLUE sulfide vat dye, fast to light, acids, washing and chlorine. 

S. 728—“Immedial Pure Blue.” Note 693,633 for salt of above dye with Ca, etc. 


693,633—Feb. 18, 1902. Arthur WEINBERG and Richard Herz, Germany. (Cassella.) 
Process of making blue sulfur dye. Purifying dye of 693,632. 

Dialkyl 4-amino 4/oxy-DIPHENYLAMIN, is treated as in 693,632 at temp. below 140°, dye pptd. 
with CaCL, salt, or other metal giving soluble sulfid, filt., washed, redissolved in Na,S and 
Na,CO,, filt. and pptd. by NaCl. Impurities and, accompanying black dyes are thus removed 
and pure BLUE dye remains. 


S. 728—“Immedial Pure Blue.” 


260 DIGEST OF PATENTS 


695,533—Mar. 18, 1902. Anton Bonati, Germany. (Kalle.) 


Sulfur dye and process of making same. 

4-Nitro 2-amino 4'-oxy DIPHENYLAMIN from dinitro comp., in alc. soln., heated with carbon 
bisulfide to form thio carbamid, then fused in sulfur melt at 110-145°. Product is sol. in aq. 
(GB), changing with Na,S to (B) and on boiling (Gt); a gray GREEN sulfide vat dye developed 
to green BLUE by H,O, and metallic salts, such as SnCl,. 

S. 736—‘‘Thionin Blue B.” Note 695,534 for process of purification, 


695,534—Mar. 18, 1902. Anton Bonati, Germany. (Kalle.) 


Sulfur dye and process of making same. 

Air is passed through the aqueous soln. of crude melt of 695,533, while salt is added in 
portions till all dye is pptd. Product is sol. in aq. (GB), turning with Na,S to (B) and on 
boiling to (pale Y-G); green BLUE sulfide vat dye, brighter and more violet with H,O, and SnCl,. 


695,835—Mar. 18, 1902. Friedrich Reuspotp, Germany. (Badische.) 


Black sulfur dye and process of making same. 

Dinitro m-dichlor BENZENE nitrated to tri comp. then boiled in alc. soln. with 4-amino 
PHENOL HCl and sod. acetate to form 4’.4”-hydroxy diphenyl 2.4.6-trinitro 3-PHENYLENE DIAMIN, 
which is heated in sulfur melt to 160-180°. Black substance, sol. in aq. (G), which with Na,S 
is bluer, sol. in conc. sulf. (dull G); green BLack sulfide vat dye, made bluer by H,O, and 
NH,OH. 

Near S. 724—‘‘Immedial Black.”’ 


696,751—Apr. 1, 1902. C. Ris, Switzerland. (Geigy.) 
Blue sulfur dye and process of making same. 

The INDOPHENOL or dimethyl 4-amino phenyl quinone imid, obtained by oxidation of as- 
dimethyl 4-PHENYLENEDIAMIN and PHENOL with hypochlorite, reduced and sulfonated with sul- 
fite, pptd. by acid and heated in sulfur melt at 120-130°, then oxidized. Blue paste or powd. 
almost insol. in aq. and Na,CO,, sol. in hot NaOH (B), diff. sol. alc., insol. ether and C,H,, 
sol. in conc. sulf. (Br), insol. dil. acids, sol. in Na,S (B), in excess (GyV), with oxygen (B); 
fast BLUE reducing sulfide vat dyes. 

Note 698,555 for use of copper and its salt in melt. 


698,220—Apr. 22, 1902. Anton PFENNIGER, Switzerland. (Brugg.) 
Greenish-black sulfur dye and method of making same. 

ToLUENE 4-Sulfo heated in Na,S melt to 130-250°, sulfur added and further heated at 
280-300°. Green BLAcK sulfide vat dye, fast to light. 


698,555—Apr. 29, 1902. C. Ris, Switzerland. (Geigy.) 
Green sulfur dye and process of making same. , 

Sulfo acid of dimethyl 4-amino 4/-oxy DIPHENYLAMIN (indophenol, from dimethyl 4-PHENYL- 
ENEDIAMIN and PHENOL treated with sulfites) heated to 125-130° in sulfur melt with copper or 
its salts. Dark powd., sol. in aq. (V), diff. sol. in alc., insol. ether and C,H,, aq. soln. pptd. 
by acids, (Br), insol. NH,OH and Na,CO,, sol. conc. sulf. (Br-GyV); GREEN sulfide vat dye, 
fast to soap and light. 

Addition to 696,751. 


701,051—May 27, 1902. Werner Ketspe, Germany. (Héchst.) 
Black sulfur dye and process of making same. ; 

Chlor nitro PHENOL sulfo or 2.6-dichlor 4-nitrophenol or other derivs. in which the NO, is 
in ortho position to halogen or takes place of sulfo group, heated in sulfur melt to 160-190°. 
Deep black powd., insol. in aq., and alk. carbonates, partly sol. in caustic, sol. in alk. sulfids; 
green BLACK sulfide vat dyes, becoming deep black with copper salts. 


701,435—June 3, -1902. Arthur WEINBERG, Germany. (Cassella.) 
Brown-violet sulfur dye and process of making same. 

2.4-Dinitro chlor BENZENE and 4-amino sALicyLic acid, condensed to form 2-amino 7-oxy 
PHENAZIN, its sulfo, halogen or carboxy deriv., then heated in sulfur melt to 140-150°. Dark 
violet or black powd., sol. conc. sulf. (VBk), pptd. on diln., sol. in alk. sulfids; brown vioLET 
sulfide vat dyes, fast to washing, alks., acids, and light. 

S. 739—‘‘Immedial Bordeaux G.” . Note 866,939 for similar process, also 818,980. 


Sanne ee ne ee eee 


GROUP XV.—SULFUR 261 


706,969—Aug. 12, 1902. Ivan Levinste1In and Carl MENnscuinc, England. 
Black sulfur dye and process of making same. 


4-NITRANILIN, 2 mols., coupled with PHENOL and resulting disazo dye refluxed in aq. soln. 
of Na,S and S. Mixed disazo dyes using one mol. nitranilin and another diazo body claimed. 
Equimol. of 4-oxy dinitro DIPHENYLAMIN added to above melt give bluer blacks. Copper sulfate, 
etc., assists reaction. Products are insol. in alc. and conc. sulf., sol. in NaOH and Na,S, (GB); 
green BLACK sulfide vat dyes, fast to washing, light. 


702,369—June 10, 1902. Ivan LkEviInsTEIN and Carl MENscuING, England. (Levinstein.) 
Black sulfur dye and process of making same. 


Dinitro PHENOL, trinitro phenol, picramic acid, or other nitro or amino derivs., heated with 
OXY azO BENZENE in soln. of sulfur in Na,S at boiling temp. or above, with or without zinc or 
other metal, pptd. by acids, bicarb., salt, or current of air. By mixtures in different propor- 
tions black dyes varying from red to violet to green black are obtained. (See table of pro- 
portions for various shades.) Black powds., insol. in aq., alc., sol. in conc. sulf., pptd. on 
diln., sol. in alk. sulfids; a red to green sLacx sulfide vat dye. 

Note 655,659. 


708,662—Sept. 9, 1902. Alcide F. Porrriger, France. (St. Denis.) 
Blue sulfur dye and process of making same. 


INDOPHENOL derived by oxidation of equimols of 4-PHENYLENE DIAMIN and PHENOL or 
cresol, is heated in aq. Na,S and S$ to 120-130°, and to this is added the product of reaction 
of 2 mols. sulfur chloride on 1 mol. PHENOL and temp. raised to 150-160° till dry. Black 
powds., sol. in aq. (B), pptd. by acids, ppt. sol. in Na,CO,, and alk. sulfide; fast BLUE sulfide 
vat dyes. 

Near S. 735—‘‘Pyrogen Indigo.” Addition to 646,873. 


709,151—Sept. 16, 1902. Richard Herz, Germany. (Héchst.) 
Blue sulfur dye and process of making same. 


4-Amino tolyl 4’-oxy DIPHENYLAMIN, is heated in sulfur melt at 80° then at 120°. By 
modifying conditions, temp., etc., the shade of color is varied,—high temp. more green, lower 
temps. more red. Dark blue powd., sol. in aq. containing caustic or alk. sulfids, (dull RV), 
sol. conc. sulf. (B); piu sulfide vat dye fast to acids, light, and milling. 

S. 733—‘“‘Immedial Indones.” Note 742,089. 


710,766—Oct. 7, 1902. Walter DotuFus, Germany. (Hochst.) 
Blue sulfur dye and process of making same. 

4-Amino 4’-oxy DIPHENYLAMIN heated in sulfur melt to 120°, pptd. by acid, washed, and 
oxidized in alk. soln. by air. Blue black bronzy powd., somewhat sol. in usual solvents; a 


“BLUE sulfide vat dye, fast when coppered. 
Near S. 728—‘“‘Immedial Pure Blue.” 


711,038—Oct. 14, 1902. Edward Cuumann, New York. (Schoellkopf.) 
Dark sulfur dye and method of making same. 

' Dinitro saLicyLic acid heated in sulfur melt to 150-180° or boiled in soln. with sulfur and 
Na,S. If condensing agent such as ZnCl, is added to melt, dyes are bluer black. Product, 


which may be purified by usual methods for sulfur dyes, is blue black solid, sol. in caustic or 
alk. sulfids (BG), in conc. sulf. (dark V); deep siacx sulfide vat dye. 


712,176—Oct. 28, 1902. Melchior BonicEer, Switzerland. (Sandoz.) 
Brown sulfur dye and process of making same. 


I.2-NAPHTHOQUINONE 4-sulfo, condensed with suLFANILIC acid to form 2-oxy 1.4-NAPHTHO- 
QUINONE 4/-sulfo phenyl 4-imid, which is heated in sulfur melt to 200-280°. Similar dyestuffs 
from related compounds are claimed. Dark brown powds., sol. in aq. (Br), unchanged by 
alks., pptd. by acids or BaCl,, insol. C,H, or C,H,CH,, diff. sol. boiling alc. (Br); Brown sulfide 
vat dyes. 

S. 747—‘“Thional Brown G.” 


712,747—Nov. 4, 1902. Arthur Wernsperc and Otto Lance, Germany. (Cassella.) 
Yellow sulfur dye and process of making same. 


3-TOLUYLENE DIAMIN melted in iron pot. in 2 parts sulfur, then temp. raised to 190° (not, 
exceeding 220°) to render soluble, and heated not above 150° with caustic alkali or Na,S. 


262 DIGEST OF PATENTS 


Water must be present. Products are sol. in dil. NaOH or Na,S, almost insol. in conc. sulf.; 
YELLOW sulfide vat dyes, fast to washing, milling and acids. 
S. 710o—‘‘Immedial Yellow D.” 


%714,542—Nov. 25, 1902. Arthur WerINBERG and Otto Lancer, Germany. (Cassella.) 


Orange-brown sulfur dye and process of making same. 

3-TOLUYLENE DIAMIN fused with sulfur at 250°, then after addition of Na,S, heated at 
110—120° to render soluble. Product is sol. in dil. alk. sulfids (OBr), pptd. by acids (Br), 
almost insol. conc. sulf.; orange BRowN sulfide vat dye, fast to washing, milling, acids. 

S. 7x11—‘‘Immedial Orange N.” Note 712,747 and 895,637 for similar processes. 


718,342—Jan. 13, 1903. Louis Haas, Germany. (Badische.) 
Sulfurized cotton-dye and process of making same. 


Dinitro BENZYL sulfo or mono nitro deriv., in aq. sulfur melt, heated to 150-200° then at 
220° to 240°. Other nitro sulfo components claimed. 4-NITROBENZENE sulfo gives yellow dye 
and dinitro deriv. a brown. Products are not easily sol. in 10 per cent Na,CO, or 50 per cent 
Na,S; BROWN to YELLOW sulfide vat dyes, fast to chroming and can be diazotized and coupled 
with 2-NAPHTHOL, etc., on fiber to give redder shades. 


722,6230—March 10, 1903. C. Ris and A. Myuius, Switzerland. (Geigy.) 
Yellow sulfur dye and process of making same, 


3-TOLUYLENE DIAMIN and FORMALIN, condensed to mono or di-formyl deriv., then with or 
without BENZIDIN, 3-toluylene diamin, or other diamins, heated in sulfur melt. Light brown 
powds., sol. on hot dil. NaOH or Na,S, (Y), insol. in alc., ether, C,H,, sol. in conc. sulf. 
(Y, milky); yvELLow sulfide vat dyes. 


723,154—Mar. 17, 1903. Richard Herz, Germany. (Cassella.) 
Blue sulfur dye and process of making same. 


4-Amino DIPHENYLAMIN and PHENOL oxidized in acetic soln. with bichromate, then heated 
in alk. soln. with Na,S to form phenyl 4-amino 4’-oxy DIPHENYLAMIN which is boiled in alc. 
soln. with sod. pentasulfid, then oxidized. Or dye may be formed in sulfur melt at 140—-150° 
by usual method. Dark blue powd., sol. in alk. sulfids (GB), in conc. sulf. (B); an indigo 
BLUE sulfide vat dye, fast to washing, acids and light. 

S. 735—‘‘Pyrogen Indigo.” 


723,448—Mar. 24, 1903. Hans Esetine, Germany. (Kalle.) 
Brown sulfur dye and process of making same. 


Amino derivatives of 3-TOLUYLENE DIAMIN or diazo deriv. of same, heated in sulfur melt 
to r10-120°, then to 200-2209. When azo deriv. is used, anilin splits off in first part of re- 
action. Products are sol. in aq., pptd. by acids, sol. in conc. sulf., insol. in alc.; red BROWN 
sulfide vat dyes, fast to soap and light, and can be diazotized on the fiber, and coupled with 
2-naphthol, 3-toluylene-diamin, or resorcin. 


727,387—May 5, 1903. Emil Kraus, Switzerland. (Basle.) 
Blue sulfur dye and process of making same. 


4-Nitroso PHENOL, or homolog, combined at 20-25° with DIPHENYLAMIN, or other alkyl- 
ated aromatic amin, in strong sulf. acid, then treated with alk. Na,S to form phenyl 4-amino 
4’-oxy diphenylamin derivs. or homolog, which is heated a) in alc. soln. containing Na,S, in 
autoclave to 150-160° or b) with Na,S without alc. in aq. suspension, with or without glycerin 
or metallic salts. Blue powds., sol. in aq. and alk. sulfids; BLUE sulfide vat dyes, fast to acids, 
milling, light. 

Near S. 728—‘‘Immedial Pure Blue.”’ 


728,623—May 19, 1903. Albrecht Scumipt and Fritz BetuHmann, Germany. (Ho6chst.) 
Blue sulfur dye and process of making same. 


as-Dimethyl 4-PHENYLENE DIAMIN, or other, condensed by oxidation with 2.6-dichlor PHENOL 
to form an indophenol which is reduced by Na,S to dimethyl 4’-amino 4-oxy 3.5-dichlor p1- 
PHENYLAMIN, which is heated at 94° in Na,S-S mixture with Giycerin and alcohol. Blue black 
powds., sol. in conc. sulf. (B), diff. sol. in alc.; snug sulfide vat dyes, bluer or more violet with 
air or oxidizing agents. 


GROUP XV.—SULFUR 263 


729,874—June 2, 1903. August L. Lasxka, Germany. (Oehler.) 
Olive-green sulfur dye and process of making same, 


Di-formyl 3-PHENYLENE DIAMIN, heated in sulfur melt containing ZnCl, to 110-275°. Color 
is not so bright without ZnCl,. Black brittle mass or powd., sol. in conc. sulf. (dull G), in aq. 
(GY), pptd. by HCl (YBr), sol. in dil. NaOH or NH,OH; brown GREEN sulfide vat dye, fast to 
light and soap. 


731,669—June 23, 1903. Edward Curmann, New York. (Schoellkopf.) 
Green sulfur dye and process of making same. 


Amino azo BENZENE (or toluene) HCl and 4-amino PHENOL condensed by heating together at 
180° then refluxed with Na,S-S soln. containing some copper sulfate, at 102-105°. Product is 
sol. in conc. sulf. (BBk), almost insol. in aq. Na,CO,; GREEN sulfide vat dye. 


732,090—June 30, 1903. Ivan and Herbert LkEvinstEIN, England. (Levinstein.) 
Blue sulfur dye and process of making same. 


Ethyl 2-tToLuipIN or homolog and 2-chlor 4-amino PHENOL in sulfuric acid soln. oxidized 
with bichromate to indophenol then reduced with Na,S to ethyl 4-amino 3-methyl 4’-hydroxy 
3/-chlor DIPHENYLAMIN, which is heated in sulfur melt to 115°, and pptd. by current of air. 
Blue substances, sol. in conc. sulf. (B), in NaOH (RV); BLUE sulfide vat dyes, fast to washing 
and light. 


735,775—Aug. 11, 1903. . Paul Juuius and Friedrich Reusoitp, Germany. (Badische.) 
Substantive sulfur dye. (Process claimed.) 


1.3-Dinitro 4.6-dichlor BENZENE, condensed in acetone or alc. soln. with KCNS or other 
thionizing agent, to form 1.3-dinitro 4.6-dithiocyan BENZENE, which is separated, purified, and 
with 4-amino PHENOL or derivs. and sod. acetate is heated in alc. to 65° to form 2.4-dinitro 
5-thiocyan 4’/-oxy DIPHENYLAMIN, Separated product is heated in sulfur melt to 90° then 160—- 
180°. Product is black substance, insol. in common solvents; BLUE reducing sulfide vat dye, 


oxidized by air, fast to washing, alks., acids. 


736,380—Aug. 18, 1903. Richard Guiry, Germany. (Berlin.) 
Blue sulfur dye and process of making same. 


4.4’-Dioxy DIPHENYLAMIN is fused with sulfur at 230-240°. A blue black powd., insol. in 
aq., sol. in caustic (B), in alk. sulfid (GB), in conc. sulf. (B); fast BLUE sulfide vat dye. . 


.736,403—Aug. 18, 1903. Oskar KaLtwassER and Max GaumeEr, Germany. (Berlin.) 


Indigo-blue sulfur dye and process of making same. 


INDOPHENOL, or homolog, is boiled in sulfur mixture containing at least 4 atoms of sulfur 
to 1 mol. Na,S and dye pptd. by oxidation with air. Products are insol. in aq., sol. in caustic 
alk. (dull GB), in alk. sulfids (B), in conc. sulf. (V); fast BLUE reducing sulfide vat dyes, after 
oxidation on fiber. 

Near S. 731—‘‘Thiophor Indigo.” Note 821,378 for similar patent. 


738,027—Sept. 1, 1903. Richard Giry, Germany. (Berlin.) 
Yellow sulfur dye and process of making same. 


Nitro diacetyl] 4-PHENYLENE DIAMIN, the meta or ortho comp. or homolog, and equal weight | 
BENZIDIN or other heavy volatile amin, is heated in sulfur at 230-240°. Yellow brown powds., 
sol. in conc. sulf. (Br), in Na,S (Y); yELLow sulfide vat dyes, fast to washing and light, fast- 
ness increased by coppering or chroming. 

Near S. 715—‘‘Thiocatechine.” 


740,465—Oct. 6, 1903. Alcide F. PorrriEr, France. (St. Denis.) 
Substantive black dye and process of making same. 


PHENOL, cresol, anilin, etc., mixed with sulfur chloride is heated to 150-165°, and product, 
together with substituted diphenylamins such as 4-amino 2-nitro 4/-oxy DIPHENYLAMIN, heated to 
170° then 200° after Na,S has been added. The ratio of NH, to OH in the substituted di- 
phenylamin must be less than 2:1. Products are sol. in aq.; blue Brack sulfide vat dyes, not 
affected by bichromate, etc. 

Note 646,873. 


204 DIGEST OF PATENTS 


741,030—Oct. 13, 1903. Richard Guiry, Germany. (Badische.) 
Green sulfur dye and process of making same. 


I-NAPHTHYLAMIN or sulfo derivs. and 4-amino PHENOL, homologs or halogen derivs., is 
oxidized to an INDOPHENOL which is boiled in sulfur and Na,S mixture containing copper sulfate, 
diluted and pptd. by current ot air. Dark green powds., insol. in aq., sol. in alk. sulfids (G), 
slightly sol. in conc. sulf. (B), in caustic alks. (G); GREEN sulfide vat dyes. " 


742,189—Oct. 27, 1903. Richard Herz, Germany. (Cassella.) 
Blue sulfur dye and process of making same. 


4-Amino 3-methyl 4’-oxy 3’-chlor DIPHENYLAMIN is added to sulfur melt at 80-100° then 
temp. raised to 115°, diluted, filtered, and pptd. by current of air. Lower temps. give redder 
and higher temps. greener shades. Dark blue powd., nearly insol. in aq. or alc., sol. conc. sulf. 
(B), sol. in alk. sulfids; green BLUE sulfide vat dye, fast to washing, acids and light. 

Addition to 709,151. 


746,926—Dec. 15, 1903. Edward Cuumann, New York. (Schoellkopf.) 
Orange to yellow brown sulfur dyes and process of making same. 


TOLUYLENEDIAMIN sulfo (2.6.4 or 2.4.5), the unreduced nitro or oxamin comp., is heated 
in shallow vessel at 120-130° with soda, sulfur and Na,S, then baked at 250°. Dark brown 
powds., sol. in aq., pptd. by acids (Br), sol. in conc. sulf. (YBr-RBr);oRANcE to yellow BROWN 
sulfide vat dyes that may be diazotized and coupled on fiber to deepen shade. 

Addition to 659,496 and 97. 


747,643—Dec. 22, 1903. Niklaus Ronecer, Switzerland. (Sandoz.) 
Blue sulfur dyestuff and process of making same. 


4-Amino 3-methyl 4’-oxy DIPHENYLAMIN is heated with sulfur and a little chromium hydroxid 
(Cr,O,.H,O) at 190-200° till H,S ceases to evolve and melt becomes thick. Without Cr the 
shade is duller and greener. Dark blue powd., insol. in aq. and alc., sol. in alk. sulfids (B), 
changed on boiling to (Br), sol. in conc. sulf. (B); BLUE sulfide vat dye, fast to alks., washing, 
light. 

Addition to 709,151. 


750,113—Jan. 19, 1904. Arthur LurrrincHaAus, Germany. (Badische.) 
Green dye. 


METHYLENE VIOLET, the acetyl deriv. or dye of 678,199, Re. 11973, is refluxed in 3 parts 
Na,S, 1.5 parts CS, and 9 parts ale. CS, may be omitted and more alc. (14 parts) used. Prod- 
ucts are sol. in dil. Na,S; creEn sulfide vat dyes changing to BLUE with bichromate. 


755,428—Mar. 22, 1904. Julius Apet and Arthur Lutrrincuaus, Germany. (Badische.) 
Blue-sulfur dye and process of making same. 


METHYLENE VIOLET or alkylated indophenol in 4 parts cryst. Na,S heated to 136° and to this 
is added about 1.5 parts PHENOL and 1 part S, temp. raised to 142°, refluxed, then diluted with 
aq., and oxidized by air. Product is sol. in caustic (B), not pptd. by air, pptd. by CO,; a BLUE 
sulfide vat dye. 


760,110—May 17, 1904. Wilhelm EmmMericu, Germany. (Hochst.) 
Orange sulfur dye. 

ToLUYLENE di-urea (from 3-TOLUYLENE DIAMIN and KCNO) is added to 3 parts fused sulfur 
at 170-180° then heated to 220-230°. Dark red brown powd,, sol. hot NaOH and Na,S (Br); 
ORANGE sulfide vat dye, fast to light, soap, carbonate and acids. 


763,193—June 21, 1904. Ernst Matus, Germany. (Hochst.) 
Blue sulfur dye and process of making same. 


sym-4”.4'"'"-Dioxy diphenyl 4.4’-diamino DIPHENYLAMIN, 3 parts, is refluxed with 8 parts Na,S, 
3.4 parts sulfur, and 4 parts GLYCERIN at 100 to 110°. Dark blue powd., insol. in usual solvents, 
sol. dil. alk. (B), in conc. sulf. and in alk. sulfide (G); BLUE sulfide vat dye. 


763,320—June 21, 1904. Alcide F. Porrrier, France. (St. Denis.) 
Process of making sulfur dyes. 


Dimethyl INDOPHENOL, or derivs. obtained by oxidizing dimethyl 4-PHENYLENE DIAMIN and 
PHENOL, is reduced in hot aq. with Na,S, dried to paste and at 120-130° equal part of product 


GROUP XV.—SULFUR 265 


of reaction of sulfur chloride on comm’! cresox, or other phenol, is added, then further heated 
at 130-160°. Table of reactions is given. Product is sol. in aq., and is a BLUE sulfide vat dye. 


764,733—July 12, 1904. Richard Laucu, Germany. 
Black sulfur dye and process of making same. 


4-PHENYLENE DIAMIN is condensed with 2.4-dinitro chlor BENZENE to form 4’-amino 2.4-dinitro 
DIPHENYLAMIN, which is heated in sulfur melt with water and glycerin to 175-180°. Using more 
glycerin, a lower temp. and longer heating are required, and without glycerin a higher temp. and 
several additions of solvent. Series of: reactions is given. Product is a piacK sulfide vat dye, 
faster when chromed or coppered. 

S. 727—‘“‘Auronal Black.’ Note 764,734 for different process using same ingredients, and 
764,735 for subsequent oxidation process. 


764,734—July 12, 1904. Richard Laucu, Germany. 
Direct cotton sulfur dye and process of making same. 


4-PHENYLENE DIAMIN is condensed with 2.4-dinitro chlor BENZENE to form 4’-amino 2.4-dinitro 
diphenylamin which is boiled in Na,S and S mixture containing water and preferably also some 
glycerin, at 115-125°. Longer heating at 120-130° gives black dye and fastness to washing in- 
creases with time of heating. Violet black powd., sol. conc. sulf. (V-B), pptd. on diln. (B), sol. 
dil. Na,S(V); violet BLUE to BLACK sulfide vat dyes. . 

S. 727—‘‘Auronal Black.’’ Addition to 764,733. 


’ 


773,346—Oct. 25, 1904. Albrecht Scumipt and Otto Ruopius, Germany. (Hochst.) 
Yellow sulfur dye and process of making same. 


3-TOLUYLENE DIAMIN is allowed to react upon 1 mol. CARBON BISULFIDE, product added to 
melted sulfur at 110-130°, containing BENZIDIN or other aromatic amin (about 0.17 mol.), then 
temp. raised to 190-220°. Resulting powder is dissolved in 2.25 parts Na,S and dried in vacuum. 
Brown powd., insol. in aq., alc., ether and C,H,; a fast YELLow sulfide vat dye. 

Near S. 712 or 716—-“‘Kryogen Yellow G or R.” 


775,570—Nov. 22, 1904. August L. Lasxa, Germany. (Oehler.) 
Dark-blue sulfur dye. (Process claimed.) 

2’.4’-Dinitro 5-chlor 4-oxy 3-methyl DIPHENYLAMIN is added to aq. sulfur melt at 80-90°, 
refluxed, then dried at 1ros—110°. Higher temp. yields blackish dye. Product is sol. in conc. 
sulf. (B), in aq. Na,S (GB), pptd. by HCl (Br); sive sulfide vat dye. 

Near S. 726—‘‘Pyrogen Direct Blue.” 


776,264—Nov. 29, 1904. Albrecht ScHMipt and Fritz BeErHmMann, Germany. (Hochst.) 
Blue sulfur dye and process of making same. 

Dimethyl 4’-amino 4-oxy 3-chlor DIPHENYLAMIN, from as-dimethyl 4-PHENYLENE DIAMIN, is 
condensed with 2-chlor PHENOL, then reduced or before reduction is heated in sulfur melt with 
glycerin and alc. to 94°. The proportion of S to Na,S in melt must be more than 1:4 Blue 
black powds., sol. in conc. sulf. (B), slightly sol. in alc. (RV fluor), almost insol. in glac. acetic; 
BLUE sulfide vat dyes. 


776,885—Dec. 6, 1904. Melchior Bonicer, Switzerland. (Sandoz.) 
Green sulfur dye and process of making same. 


4'-Tolyl 4”-oxy phenyl 4-NAPHTHALENE DIAMIN 6-, 7- or 8-sulfo derived from aryl 1-naphthyl- 
amin 5-, 6-, 7- or 8-sulfo acid is condensed with 4-amino PHENOL or its chlor deriv., heated with 
alkali polysulfides with or without Cu powder or salts, in alc. soln. or in presence of glycerin. 
Products are sol. in aq. (BG-YG), pptd. by acids (B), by caustic in excess (B), sol. in conc. 
sulf. (GyB), pptd. on diln. (B); Green sulfide vat dyes, fast to alks. and acids. 

S. 46—‘“Thional Green B.” Note 675,585. 


77'7,.323—Dec. 13, 1904. Julius Ase, and Arthur LurrrincHaus, Germany. (Badische.) 
Blue dye and process of making same. 


METHYLENE VIOLET or its analogs, is dissolved at 10° in 7 parts 23 per cent fuming sulf. 
one part S,Cl, added and warmed to 30-35° then separated, and product heated in sulfur melt 
to 170°. Soln. of dried melt may be used as such or pptd. by oxidation with air, filt., etc. 


266 DIGEST OF PATENTS 


Products are BLUE to blue vioLeT sulfide vat dyes, B being insol. in CHCl, and HCl while A 
is diff. sol. in CHCl, (B-BV non-fluor) and sol. in conc. HCl (B). 
Near S. 729—‘‘Kryogen Pure Blue R.”? Addition to 679,199. 


778,478—Dec. 27, 1904. Karl Exvset, Germany. (Kalle.) 
Blue sulfur dye and process of making same. 


Chlor 1-NAPHTHOL and as-dimethyl 4-PHENYLENE DIAMIN, or other para diamin of benzene 
series, 1 mol. each in 40° NaOH, is mixed with NaOCl soln. to form INDOPHENOL, which is 
separated and reduced in 1o per cent soln. of Na,S to a phenyl NAPHTHYLAMIN deriv., and 
separated product fused in sulfur melt at 110°. Dark blue powds., insol. in aq., sol. in alc. (B), 
in dil. Na,S; green BLUE to vIOLET sulfide vat dyes. 

S. 731—“Thiophor Indigo.” 


778,713—Dec. 27, 1904. Albrecht Scumipt, Germany. (Hoéchst.) 
Violet sulfur dye and process of making same. 


PHENOSAFRANINONE formed by decomp. PHENOSAFRANIN, is heated in sulfur to 190° with 
or without naphthalene as solvent and ANILIN, dimethyl anilin, phenol, or other, to form homolog 
of bluer shade. Violet black powd., insol. in aq., sol. conc. sulf. (VBk), in alk. sulfide (VR); 
VIOLET sulfide vat. dyes, bluer and faster when coppered, brighter when steamed. 

Near S. 729—‘“‘Kryogen Pure Blue.” 


779,860—Jan. 10, 1905. Arthur Litrrincuaus, Germany. (Badische.) 
Violet sulfur dye and process of making same. (Process not claimed.) 


2.6-Dichlor INDOPHENOL is heated to 120° in mixture of 4 parts Na,S, 4 parts aq., and 0.5 
part sulfur, refluxed till indophenol disappears, diluted and oxidized. Dark powds., sol. conc. 
sulf. (B), in dil. Na,S (V); green Gray to blue Gray sulfide vat dyes. 


782,905—Feb. 21, 1905. Richard Grey, Germany. (Berlin.) 
Orange sulfur dye and process of making same. 


3-TOLUYLENE DIAMIN and 1 mol. diformyl 4-PHENYLENE DIAMIN (by action of formic acid on 
4-phenylene diamin) are heated in sulfur at 200-220°. Yellow powd. insol. in aq. and alc., in dil. 
Na,S, (BrY); orange YELLOw sulfide vat dye, fast to washing and light. 

Note 813,643. 


785,675—Mar. 21, 1905. August L. Lasxa, Germany. (Oehler.) ~ 
Orange sulfur dye and process of making same. 

Acetyl TOLUYLENE DIAMIN is coupled with diazotized ANILIN or other volatile aromatic amin 
and resulting dye melted with S and BENZIDIN or other base of diphenyl series, at 220-240°. 
Melt may be dissolved in aq. and pptd. with acid, or heated to 100° with Na,S and dried. Red 
brown powd., insol. in ale. or alk. carbonate, slightly sol. conc. sulf. and dil. caustic, sol. in 
alk. sulfide (YBr); orange YELLOW sulfide vat dyes. 


790,167—May 16, 1905. Julius AsEL and Arthur LutrrincHaus, Germany. (Badische.) 
Blue sulfur dye and process of making same. 

Phenyl 4-amino 4’-oxy DIPHENYLAMIN, dichlor deriv., or other, is heated in strong NaOH 
soln. at 165°, sulfur added and heated again at 165-175°, more sulfur added and heated to 


180-185°, dissolved in Na,S and pptd. by oxidation with air. Products are sol. in hot Na,S 
(Yt); BLUE to VIOLET reducing sulfide vat dyes, oxidized on fiber. 


796,443—Aug. 8, 1905. Theodor MucHatt, Germany. (Kalle.) 
Red-violet sulfur dye and process of making same. 
ANILIN azO I-NAPHTHYLAMIN is boiled in strong HCl soln. with 4-amino PHENOL to form 


poly oxy ROSINDULIN which is heated in sulfur melt to 160°. Product is sol. in Na,S (VR), in 
conc. sulf. (B); a red vIOLET sulfide vat dye. 


796,514—Aug. 8, 1905. Julius Horriein, Germany. (Weiler-ter-Meer.) 
Process of making a yellow sulfur dye. 
Nitro a-methyl BENZIMIDAZOLE, or amino deriv., and 1 mol. BENZIDIN are heated in 4 parts 


sulfur at 200-240°. Product may be dissolved in Na,S. Process compared with similar patents 
of numbers not shown. A green YELLOW sulfide vat dye. 4 


GROUP XV.—SULFUR 267 


8$01,598—Oct. 10, 1905. August L. Lasxa, Germany. (Oehler.) 
Brown sulfur dye and process of making same, 


RESORCIN and FORMALDEHYDE are condensed to form METHYLENE diresorcin then with 3- 
PHENYLENE DIAMIN or other meta diamin of benzene series heated in sulfur melt to 170—-220°. 
Black powds., sol. in conc. sulf. (YBr), in dil. Na,S (Br), pptd. by HCl (Br); fast Brown 
sulfide vat dyes. 


802,049—Oct. 17, 1905. Ivan LEvINsTEIN and Ernest E. Nasr, England. 
Green-blue sulfur dye and process of making same, 


4-Nitroso PHENOL 4-nitroso 2-cresol or ortho chlorine comps. of same is added to sulfuric 
acid soln. of an amino sulfo acid of benzene or naphthalene having free para amino positions, 
such as CLEVE’s acid, then pptd. by sod. carbonate, reduced by Na,S, heated with polysulfids 
to 110—-120°, and finally oxidized. If temp. is kept below 100° bluer shades result. 


Products are insol. in aq. and usual solvents, sol. conc. sulf. (GB); green BLUE reducing 
sulfide vat (Gy B) dyes. 


813,643—Feb. 27, 1906. Richard Grey, Germany. (Berlin.) 
Orange-yellow sulfur dye and proeess of making same. 


4-PHENYLENE DIAMIN and 1 mol. diformyl 3-TOLUYLENE DIAMIN, are melted with sulfur at 
250°. Patent compares product with dye from closely related component. Brown red powd., 
fusol, ie ad., alc. sol. in NaOH (CY), pptd. by HCl (YBr), sol. in Na,S (Y); orange YELLOW 
sulfide vat dye, fast to washing and milling. 

Addition to 782,905. 


818,980—Apr. 24, 1906. Albrecht ScuMip?t, Germany. (Hochst.) 
Sulfur dye and process of making same. 


2-Amino 7-Oxy PHENAZIN HCl or other hydroxylated azin, is heated with alk. polysulfide 
containing CuSO, at 110°, then refluxed. Methyl and Cl derivs. of above, N_ substituted 
safraninones and derivs., etc., and copper or Cu,S equivalents, also claimed. Products are sol. 
in hot Na,S; rep, dark RED to vioLET sulfide vat dyes changing to BLUE when coppered on fiber. 
Note 829,740. 


820,501—May 15, 1906. Paul Junius and Eduard Mincu, Germany. (Badische.) 
Green-blue sulfur dye and process of making same. 


CHLORANIL together with as-dimethyl 4-PHENYLENE DIAMIN thio sulfo are heated at 65 to 
75° in aq. soln. containing Na,S, soda and sulfur. Mercaptans and disulfids may be used for 
thio sulfo comps. and diethyl deriv. also. Violet black powds., slightly sol. hot aq., (B), sol. 
conc. sulf. (BG), in hot Na,S (YBr), slightly sol. in CH;NH, (G), in C,H.OH (GB), insol. glac. 
acetic, alc., acetone, contains no Cu; green BLUE sulfide vat dyes, fast to washing, light, Cl. 


821,378—May 22, 1906. C. Ris, Switzerland. 
Blue sulfur dye and process of making same. 


as-Dimethyl 4-PHENYLENE DIAMIN, or other para diamin, and 1-NAPHTHOL, are condensed to 
form INDOPHENOL which is heated in sulfur mixture at 115°, then dissolved in aq. and oxidized 
by air or pptd. in leuco form. Dark blue powd., insol. in aq., sol. in alc. or C,H, (B), sol. in 
Na,S (G), in conc. sulf. (Br), and decomp.; BLUE to VIOLET sulfide vat dyes. 

S. 731—‘“Thiophorindigo.” 


829,740—Aug. 28, 1906. Albrecht Scumipt, Germany. (Hoéchst.) 
Bordeaux-red sulfur dye and process of making same. 

Ethyl tolu-sAFRANINONE HCl, or other safraninone of fatty series, is refluxed at 110 to 135° 
with Na,S and S. Higher temp. gives bluer products. Glycerin may be used. Bordeaux RED 
sulfide vat dyes changing to vIOoLET when coppered. 

Note 701,435 for related dye, and 818,980. 


841,877—Jan. 22, 1907. August L. Lasxa and Georg List, Germany. (Griesheim.) 
Blue sulfur dye and process of making same. 


4-Amino PHENOL and 2-chlor methyl ANILIN, or homologs, are oxidized to INDOPHENOL by 

bichromate in H,SO, soln. keeping below O°. On reduction in alk. soln. product gives 4’-oxy 

methyl 4-amino 3-chlor DIPHENYLAMIN, which is heated with polysulfids to 115°. Dark violet 
18 


268 DIGEST OF PATENTS 


powds., almost insol. in aq., alc., C,H, and glac. acetic, sol. hot glycerin and conc. sulf. (darkB), 
in dil. Na,S (V); BLuE sulfide vat dyes, fast to washing, light, acids. 


843,156—Feb. 5, 1907. August IL. Lasxa, Germany. (Griesheim.) 
Green sulfur dye. (Process claimed.) 


4-Amino PHENOL is mixed in alk. soln. with 1 mol. 1-naphthol 4-rotyzt sulfonamid, cooled and 
condensed, by adding hypochlorite, to an indophenol which may be reduced with Na,S to phenyl 
naphthylamin deriv. The INDOPHENOL or its leuco paste is heated at 120° with alk. polysulfids 
containing copper powder and CuSO, Dark green powds., diff. sol. in aq., sol. conc. sulf. (B), 
in Na,S(G); GREEN sulfide vat dyes, fast to washing. 


864,644—Aug. 27, 1907. W. Herzperc, O. SCHARFENBERG and M. Ronus, Germany. (Berlin.) 
Sulfur dye and process of making same. 


4-Tolyl sulfo 4-amino 4’-oxy DIPHENYLAMIN, chlor deriv. or analogous comps., is boiled with 
alk. polysulfids, diluted and pptd. by air, then treated with conc. sulfuric acid to remove the aryl 
sulfo group. Dark bronzy powds., insol. in aq., boiling dil. NaOH and usual organic solvents, 
sol. in conc. sulf. (B-V), pptd. on diln.; sLux sulfide vat dyes, that need not be coppered to be 
fast to washing, light, and acids. 


866,939—Sept. 24, 1907. Fritz LEHMANN, Germany. (Bayer.) 
Reddish-brown sulfur dye. 

4-Amino PHENOL and 3-TOLUYLENE DIAMIN with NH, and MnO, etc., are condensed to form 
amino oxy TOLU-PHENAZIN, whish is heated with sulfur and Na,S to 135°. Dark brown powd., 
sol. dil. Na,S (dark Br), insol. in 27 per cent NaOH, sol. conc. sulf. (dark Br ), pptd. on diln. 
(RBr); red Brown sulfide vat dye remaining brown when coppered. 

Near S. 739—‘‘Immedial Bordeaux G.” Note 701,435 and 818,980. 


886,532—May 5, 1908. Miles R. Morrart and Harry S. Spira, Rhode Island. 
Brown sulfur dye and process of making same. 


Crude woop Tar is treated with alkali to remove phenols and cresols, and residual tar 
heated in sulfur melt not to exceed 200° until dry. Product is partly sol. in aq., sol. in alk. 
sulfids, pptd. by acids; Brown sulfide vat dye, fast to light, scouring and cross dyeing. 


889,936—June 9, 1908. Georg List, Germany. (Griesheim.) 
Brown sulfur dye and process of making same. 
2.4-Dinitro chlor BENZENE or other aromatic m-dinitro compound and GLYCERIN are heated 


with alk. polysulfids to 200-240°. List of components and color of resulting dyes given. Gray 
brown powds., sol. in aq. (Br), pptd. by HCl (Br); Brown sulfide vat dyes. 


8§92,455—July 7, 1908. Werner Scumipt, Germany. (Cassella.) 
Yellow sulfur dye and process of making same. 


Dehydro thio TOLUIDINE, or analogous compounds such as primulin bases and BENZIDIN or 
thio benzidin, is heated with sulfur to 210° then Na,S added and again heated to 120-125° till 
sol. in aq., diluted and pptd. with HCl. Brown powds. insol. in ag., acids or organic solvents, 
sol. conc. sulf. (YGy), pptd. on diln. (Br), sol. conc. NaOH (YBr), sol. in Na,S; green YELLOw 
sulfide vat dyes. 


893,499—July 14, 1908. Benno Homoika and Robert WeEtpE, Germany. (Hochst.) 
Process of making sulfur dyes and their leuco bodies. (Process classed as dye.) 

Two mols. 2-thio aceto phenones united as dithio comps. 

2-Thio ACETOPHENONE or deriv., obtained from amino comps., is oxidized by air or other 
agent in alk. soln. Products must be reduced to leuco form for dyeing. Or dyes can be 
prepared in leuco form by melting thio acetophenone in Na,S, adding sulfur and heating until 
about one half water of crystn. of Na,S has evaporated. When oxidized same dyes as above 
result. They are insol. in usual solvents, reduced by alk. agents; violet Brug sulfide vat dyes. 


895,637—Aug. 11, 1908. Alfred Herre and Bernhard JarcKet, Germany. (Bayer.) 
Brown sulfur dye. 


3-TOLUYLENE DIAMIN, or other meta diamin, and 3-NITRANILIN or other meta amin, are 
heated in sulfur to 240-250° then boiled in Na,S soln. One component must be alkylated in 


GROUP XV.—SULFUR 269 


nucleus. Dark powds., insol. in aq., sol. dil. Na,S (Br), diff. sol. NaOH and conc. sulf. (Br); 
yellow-BROWN to ORANGE sulfide vat dyes. List of components and colors of resultant dyes is 
given. 


Near S. 711—‘‘Immedial Orange B.” Note 714,542 for patent with similar process, and 
896,916. 
$96,916—Aug. 25, 1908. Bernhard JAECKEL, Germany. (Bayer.) 


Yellowish-brown sulfur dye. 


3-TOLUYLENE DIAMIN or Other aromatic meta diamin or triamin and 3-NITRANILIN or other 
nitro amin, are heated with BENZIDIN in sulfur to 240-250° then boiled in Na,S soln. One 
component must be alkylated in the nucleus. Yellow brown powds., insol. in aq., sol. dil. Na,S, 
(YBr), diff. sol. NaOH (YBr); vELLOW to ORANGE sulfide vat dyes. 

Homolog of S. 711—“‘Immedial Orange N.” Addition to 895,637. 


897,873—Sept. 8, 1908. Emile T. Bunpsman, California. (Pt. Loma.) 
Sulfur dye and process of making same. 


SUGAR, grape sugar, glucose, cane sugar, etc., is heated in sulfur melt with or without 
3-NITRANILIN, 3-phenylenediamin, sulfanilic acid, benzidin, diphenylamin, or other compounds, 
that may or may not themselves give rise to dye. Dark. powd., sol. in aq., alc., Na,CO, and 
NaOH; a dark Brown sulfide vat dye, which when heated with HCl forms another coloring 


“matter insol. in aq., etc., sol. in Na,S soln., also a dark Brown sulfide vat dye. 


Modification of S 706—‘‘Cachou de Laval.” 


899,845—Sept. 29, 1908. Alfred ScHAARSCHMIDT, Switzerland. (Basle.) 


Orange to orange-yellow wat dye and process of making same. A sulfur 
containing anthraquinone deriv., probably a thiazin indanthrene. 


2-Methyl ANTHRAQUINONE or halogenated derivs. with halogen in nucleus heated to 290—-300° 
then at 320-330° in sulfur, then oxidized by hypochlorite. Orange to brown yellow powds., sol. 
in cone. sulf. (V-VB) in 24 per cent fuming acid (G); ORANGE to orange YELLOW vat dyes fast 
to washing, light, Cl. 

Note 902,895. 


901,970—Oct. 27, 1908. Gustav E. Junius, Germany. (Sanderson.) 
Black sulfur dye and process of making same. 

Nitroso 2-crEsot boiled in aq. soln. of Na,S and S. It is better to treat first with dilute 
sulfide soln., separate product and treat again with stronger Na,S and S. Product must be pptd. 
from soln. not evap. to dryness. It is insol. in aq., acids, alk. carb., sol. in alk. sulfids; a 
green BLACK sulfide vat dye, fast to Cl, light, milling, alkalies, acids, cross dyeing. 


902,895—Nov. 3, 1908. Bertram Mayer and A. ScHaarscHMip?, Switzerland. (Basle.) 
Orange-to-yellow wat dye and process of making same. Probably an N-dichlor- 
methyl thiazin indanthrene. 
w-Dichlor methyl ANTHRAQUINONE (containing some monochlor) or related comp., is heated 
with sulfur, purified and treated with aik. hypochlorite. Orange to yellow powds., sol. in conc. 
sulf. (dull R-RV), in 24 per cent oleum (BkG-BrG); yELLow vat dyes, fast to washing, light, Cl. 
S. 7o5—‘“‘Cibanon Yellow R.” Addition te &99,845. 


904,809—Nov. 24, 1908. Erich Saunt, Germany. (Cassella.) 
Yellow-olive dye and process of making same. 


4-PHENYLENE DIAMIN heated in 2 parts sulfur with 3-PHENYLENE DIAMIN to 200-240°, cooled, 
pulverized and heated at 115° in 3 parts Na,S till aq. sol., diluted and pptd. by acids, by air, 
salts of lime or NH,. Or 3-phenylene diamin may be heated with S to form thio compound then 
para salt added. Dark powd., insol. in neut. or acid liquids, sol. in alk. sulfids; fast green 
BRowN sulfide vat dye. 


904,224—Nov. 17, 1908. Alcide F. Porrrier, France. (St. Denis.) 
Process of making black sulfur dyes. 


Dinitro pHENoL, Na salt, instead of fusing with polysulfids is boiled in polysulfid soln. 
of definite compos. for long time, raising temp. to 106-108° by addition of salts to soln., the 


270 DIGEST OF PATENTS 


proportion of polysulfid being such that the dyestuff as formed separates as a ppt. <A black powd., 
insol. in aq., alc., and sulf., even when fuming, sol. in Na,S (B); a blue Biacx sulfide vat dye. 
S. 723—‘‘Autogene Black EEB.”’ Process classed as dye by Schulz. 


909,151—Jan. 12, 1909. Edward S. Cuapin, New York. 
Sulfur dye and process of making same. 


Non crystallizable ponysaccHaRiIps (starches, dextrins, gums, sawdust, etc.), are heated in 
sulfur melt at such temp. and for such time that product when dry is pulverizable and non- 
hygroscopic. Products are sol. in aq., alc, NaOH and Na,CO, and when pptd. by acids are 
insol. in aq. or alc., sol. in Na,S; yellow Brown sulfide vat dyes, fast to alkalies, acids, fulling 
and when treated with Cu salts, faster to light. 

Modification of 706 or 708—‘‘Cachou de Laval.” 


909,152—Jan. 12, 1900. Edward §S. Cuapin, New York. 
Sulfur dye and process of making same. 


Non crystallizable poLySACCHARIDS (starches, dextrins, gums, sawdust, etc.) are heated in 
sulfur melt at 300° with 3-PHENYLENE DIAMIN, or other aromatic chemical. Products are sol. 
in aq. or alc. (Br), sol. in NaOH or Na,CO,, when pptd. by acids are insol. in aq., or alc., 
but sol. in Na,S; cutch Brown sulfide vat dyes, fast to alkalies, acids and fulling, faster to 
light when chromed, especially if CuSO, is present in bath or is added to fiber. 

Addition to 909,151. 


909,153—Jan. 12, 19009. Edward S. Cuapin, New York. 
Sulfur color and process of making same. 


Noncrystallizable PpoLysaccHaRIpDS (starches, dextrins, gums, sawdust, etc.) are heated in 
sulfur melt with 3-PHENYLENE DIAMIN, or other aromatic chemical, using an excess of sulfur in 
the melt more than Na,S will dissolve. Product is sol. in aq., in alk. or alk. sulfids (Br), in 
alc. (YBr), when pptd. by acids is insol. in aq., alc., but is sol. in Na,S (Br); Broww sulfide vat 
dyes, fast to alkalies, fulling, faster when coppered. 

Addition to 909,151. 


909,154—Jan. 12, 19009. Edward §. CuHapin, New York. 
Sulfur dye and process of making same. 


SALICYLIC acid, Na salt, or other equivalent, is heated in sulphur melt at 300° for 3 hours. 
Product is sol. in aq., alc., alks., alk. sulfids (YBr), when pptd. by acids is insol. in aq., alc., but 


sol. in Na,S (YBr); yellow Brown sulfide vat dye, fast to light, fulling and faster after being 
treated by metals. 


909,155—Jan. 12, 1909. Edward §. Cuapin, New York. 
Sulfur dye and process of making same. 


CARBOHYDRATE, such as starch, is heated in sulphur melt with CuSO, to 140° and then 190°. 
Product is sol. in aq.. NaOH, Na,CO,; brown siack sulfide vat dye, fast to light. 
Modification of S. 706—‘‘Cachou de Laval.” 


909,156—Jan. 12, 1909. Edward S. Cuarin, New York. | 
Sulfur color and process of making same. 


3-PHENYLENE DIAMIN or other aromatic chemical is added to fused sulfur melt, followed by © 
starch or other carbohydrate and CuSQO,, heated to dryness, temp. raised to-140° then to 300- 
350°. Products are sol. in aq., NaOH, Na,CO,(RBr); red Brown sulfide vat dyes. ‘ 


909,277—Jan. 12, 1909. Emil T. Bunpsman, California. (Pt. Loma.) © 
Sulfur color and process of making same. 4 


GRAPE SUGAR mixed with Na,S and S, is heated to 120°; cooled, dissolved, 1-mol. 3-NITRANILIN 
added, dried, and temp. raised to 250-300°. Other color-forming aromatic chemicals are claimed, ° 
including some which, when sulfured without sugar, will not produce a dye. Products are sol. 


in aq. and alk. carb., when pptd. by acids are insol. in aq., alc., alk. carb., and conc. sulf., slowiag 
sol. in caustic, sol. in Na,S; fast BLUE sulfide vat dyes. 


919,572—Apr. 27, 1900. Louis Haas, France. (Cassella, N. Y.) 
Blue sulfur dye and process of making same. 


CARBAZOLE dissolved in conc. H,SO, is added to H,SO, soln. of nitroso PHENOL, keeping 


GROUP XV.—SULFUR 271 


temp. below 30°, diluted, filt., product boiled with Na,S, then fused in sulfur melt. Dark blue 
powd., sol. conc. sulf. (GBk); fast sive sulfide vat dye. 
S. 748—“Hydron Blue R.” Note 931,598 (B) and 956,348 (Cass). 


922,282—May 18, 1909. Max IsuER, Germany. (Badische.) 
Anthracene dye and process of making same. Probably thiazin indanthrene deriv. 
ANTHRACENE or any unoxidized deriv., is heated at 250° in 3 parts S. or at 350-360°, when 
a green dye results. A metal or its oxides, hydroxides, or salts may be present to aid reaction 
or modify shade. Products are insol. in aq., in alk., dil. acids, and in common organic solvents; 
green YELLOW to BROWN vat (Br-B) dyes. 
S. 791—“‘Indanthrene Olive G.”’ 


927,868—July 13, 1909. Bertram Mayer and Adolf PrannenstreL, Switzerland. (Basle.) 
Sulfur vat dye and process of making same. 


2-Methyl BENZANTHRONE is heated with 5 parts sulfur at 200-240°. Varying temp. and 


proportions of sulfur melt produce different shades. Black powds. sol. in conc. sulf. (VR), in 
fuming acid (BrBk-VBk), diff. sol. C,H;NO, (R-BrR); GREEN to BLACK vat (BrG) dyes. 


931,598—Aug. 17, 19009. Louis Haas, Germany. (Badische.) 
Sulfur dye and process of making same. 


CarBAZOLE dissolved in conc. H,SO, is added to H,SO, soln. of 4-nitroso PHENOL, chlor. deriv. 
or other paraoxy nitroso comp., keeping below 40°, product reduced in Na,S soln. and heated 
with polysulfids. Gray to dark powds.; BLUE to vioLET sulfide vat dyes, fast to Cl, washing, 
light. 

S. 748—“Hydron Blue R.”’ (C). Note 956,348 for similar process and same components. 
Addition to 919,572. 


934,302—Sept. 14, 1909. Richard Guiry and Paul Diererye, France. (Berlin.) 
Brown sulfur dye. 


2-Amino PHENOL mixed with 2 mols. 3-ToLUYLENE DIAMIN, is heated in sulphur at 250°, 
dried melt dissolved at 1o0o-120° in 50 per cent Na,S and pptd. by acid. Proportions of 
components and of sulfur melt when yaried produce different shades. Dark powds., sol. in alk. 
sulfids (BrR), diff. sol. aq., NH,, and NaOH (O), insol. alc. and conc. sulf.; fast BRowNn 
sulfide vat dyes. 

Note 934,303. 


934,3038—Sept. 14, 1909. Richard Gury and Paul Digrerie, France. (Berlin.) 
Olive sulfur dye. 
4-Amino PHENOL, 2 mols. and 1 mol. 3-TOLUYLENE DIAMIN are heated in sulfur to 250°, cooled, 
powd., and boiled in 50 per cent Na,S soln. Proportions of components and of sulfur when 
varied produce different shades. Gray powds., sol. in alk. sulfids (Br), diff. sol. aq. and conc. 
NH,, sol. in NaOH (G), insol. in alc. and conc. sulf.; brown GrEEN (olive) sulfide vat dyes. 
Addition to 934,302. 


935,009—Sept. 28, 1909. Joseph FLACHSLAENDER, Germany. (Bayer.) 
Sulfur dye. 

2.4-Dinitro 6-chlor PHENOL, heated at rro-115° in Na,S and S. Black powd. insol. in aq., 
and conc. sulf., sol. in 30° NaOH (B), and in Na,S(BG); Brack sulfide dye. 


956,348—Apr. 26, 1910. Richard Herz, Germany. (Cassella, N. Y.) 
Blue vat dye and process of making same. . 

4-Nitroso PHENOL condensed with cARBAZOLE, is boiled with polysulfids of high sulfur con- 
tent, preferably in a suitable solvent such as alcohol, and freed from excess S by boiling in 
Na,S. Dark blue powd., of metallic luster, sol. conc. sulf. (dark G), and in Na,S (Y), insol. 
in usual organic solvents; deep BLUE sulfide vat dye. 

Near S. 748—‘“‘Hydron Blue R.” Note 919,572, 931,598 and 966,092 for same components 
and similar processes. 


958,640—May 17, 1910. Rudolf Haucwitz, Germany. (Berlin.) 
Sulfur dye and process of making same. (Process not claimed.) 

2-TOLUIDIN, or deriv., is heated in sulfur at 220-240° with 4-PHENYLENE DIAMIN, or 
4-nitranilin, and melt boiled in a large volume of 2:1 soln. of Na,S in aq. Dark green to black 


272 DIGEST OF PATENTS 


powds., insol. in aq. or alc., partly sol. hot NaOH, sol. in Na,S (BrG), insol. conc. sulf.; brown 
GREEN sulfide vat dyes, fast to washing and light, dulled by after chroming or coppering. 


960,652—June 7, 1910. Georg List, Germany. (Griesheim.) 
Brown sulfur dye and process of making same. 


2-Nitro PHENOL, 2 mols., is condensed with FORMALDEHYDE to form dinitro dioxy pIPHENYL 
methane, which is heated with polysulfids containing CuSO, to a) 100-110° or b) to 190-210°. 
Products are sol. in alk. sulfids (V), in conc. sulf. (Br); red to violet Brown sulfide vat dyes, 
fast to light and milling, the b) product being yellower than a). 


960,919—June 7, 1910. Richard Herz and Erich Saut, Germany. (Cassella, N. Y.) 
Blue sulfid colors and process of making same. 


Dimethyl 4-amino 4’-oxy DIPHENYLAMIN, or other leuco indophenol or indophenol, is con- 
verted into sulfid color then halogenated in formic acid soln. Dark blue powds., insol. in aq., 
alc., diff. sol. hot phenol (VB-B), sol. in alk. sulfids; violet BLUE to BLUE sulfide vat dyes, 
fast to washing, light and especially Cl. 


961,387—June 14, 1910. Paul THoMASCHEWSKI, Germany. (Bayer.) 
New wat dye. Anthraquinone derivs. containing sulfur. 


1-Amino ANTHRAQUINONE 5-sulfo acid is heated in an autoclave at 170° for 10 hours with 
2 parts sulfur, 10 parts Na,S and 8 parts aq. Anthraquinone mercaptans or derivs. yielding 
mercaptans with alk. polysulfides are included in claims. Brown to black powds. insol. in aq., 
alks., alk. sulfids and organic solvents; green BROWN to GRAY to brown BLACK vat dye. 

Note 961,388. 


961,38S—June 14, 1910. Paul THomMascHEWSKI, Germany. (Bayer.) 
Vat dye. 


ANTHRAQUINONE 1.5-dimercaptan in 8 parts molten sulfur is heated to 300°. Alfa or beta 
mercaptan, dimercaptans and alkyl derivs. are included in claims. Brown to black powds., insol. 
in aq., alk., alk. sulfids, and organic solvents; green BROWN to GRAY to brown BLACK vat dyes. 

Addition to 961,387. 


966,092—Aug. 2, 1910. Richard Herz, Germany. (Cassella, N. Y.) 
Indophenolic compound and process of making same. 


N-Ethyl cArBAZOLE, or other N-substituted carbazole, is condensed in H,SO, soln. with 
4-nitroso PHENOL to form INDOPHENOL which may or may not be reduced to leuco form, then 
is treated with alk. polysulfids, either in aq. soln., with or without glycerin, or in alc. soln., 
or leuco base is melted with sulfur. If high percentage of sulfur is present, a blue dye faster 
than indigo results. Dark blue powds., of metallic luster, insol. aq., alc., sol. in hot phenol (B), 
sol. alk. sulfids; BLUE sulfide vat dyes, fast to washing, light, and bleaching. 


966,47S8—Aug. 9, 1910. Alfred ScHAARSCHMIDT, Switzerland. (Basle.) 
Orange sulfur dye and process of making same. 


2-Methyl ANTHRAQUINONE or its omega chlor deriv., is heated with S at 250-300°, cooled 4 
and heated to 140-150° with H,SO,, product separated and treated with hypochlorite. Brick red 
powds.; ORANGE reducing sulfide vat (RBr) dyes, fast to washing, light, chlorine. 


996,485—June 27, 1911. Wilhelm Hrrzperc and Walter Brucx, Germany. (Berlin.) 
Sulfurized wat dye of the anthraquinone series. 


6-Amino anthraquinone 1.2-phenyl THIAZOLE, derived by sulfur treatment of mono benzylidin 4 
2.6-diamino ANTHRAQUINONE, is refluxed in acetic anhyd. and acetylated comp. separated by 
filtn. Other organic residues, such as formyl, benzoyl, phthalyl, etc., may be introduced. Yellow 
powd., insol. alc. C,H, and glac. acetic, sol. in C,H;NH,, pyridin, C,H;NO,, and conc. sulf. (Y), — 
pptd. on diln. (Y), sol. fuming 25 per cent sulf. (BrR); yeLLow sulfide vat dye. Warmed in ~ 
conc. sulf. and deprived of acetyl group, this first dye yields an orange YELLOW sulfide vat dye é 
that may be diazotized and coupled on fiber. (With 2-NAPHTHOL it gives a BROwN color.) 


999,045—July 25, 1011. A. I. Lasxa, Germany. (Griesheim.) & 
Manufacture of brown sulfurized vat dyestuffs. (Products claimed.) 7 


1.5-Dinitro ANTHRAQUINONE or diamino deriv., is heated to 200° in autoclave with alk. 
polysulfids until insol. in Na,S soln. Temp. and proportions of sulfur melt may be varied. 7 


GROUP XV.—SULFUR 273 


Black powds., insol. in aq., alc., NaOH, and Na,S; green Brown hydrosulfite vat dyes. 
Near S. 749—“‘Anthraquinone Black.’’ Note 597,983 for related dye. 


1,026,881—May 21, 1912. Otto Rernuarp?r and Julius Horrtin, Germany. (Weiler.) 
Process of manufacturing black sulfurized coloring-matters. 

Dinitro PHENOL 4’-oxy 2.4-dinitro diphenylamin or other aromatic nitro hydroxy comp., is 
heated in aq. soln. with 1.5—2.5 mols. Na,S and S under pressure. Process uses less polysulfid 
and gives purer and stronger dye as a ppt. which may be readily filt. siacx sulfide vat dyes. 


S. 722—“‘Auronal Black N.” Note that patent is process only, yet Schulz credits it as a dye. 


1,053,.676—Feb. 18, 1913. Bertrand S. SummeErs, Michigan. 
Dye and process for preparing the same. (Process only claimed.) 

Azoxy STILBENE disulfo or “Curcumin S,”’ obtained by heating 4-nitro TOLUENE sulfo with 
conc. NaOH, or similar dye, is fused with Na,S, or heated in aq. Na,S. Dye can be formed in 
dye-bath just before application to goods. From 3 to 5 per cent bichromate in dye bath is 
beneficial. Fast rEp sulfide vat dye. 


1,054,88S8—Mar. 4, 1913. Hugo Wo.uFr, Germany. (Badische.) 
Blue-green vat coloring-matter. Benzanthrone thio-xanthone deriv. 

Nitro methyl BENZANTHRONE is heated to 220-240° in 4 parts sulfur until H,S ceases to 
evolve, excess sulfur removed from melt by Na,S or CS,. Dark brown powd., sol. in conc. 
sulf (BrR), in fuming (23 per cent SO,) (dull V), in C,H,;NO,(G); fast blue crEEN hydrosulfite 
vat dye. 


1,061,714—May 13, 1913. Hugo Wo.tFr, Germany. (Badische.) 
Dyes containing sulfur and process of making them. 

2.7- or 4.5-Dinitro PHENANTHRAQUINONE or other nitro deriv., is heated in autoclave at 
180-220° with equal parts sulfur, 3 parts Na,S and 5 parts aq. Conditions of melt may be 
varied. Products are insol. in acids, alks., sol. in Na,S and hydrosulfite; fast Brown reducing 
sulfide dyes, that will not couple on fiber. 


For manufacture of quinone see Ber. 36, 3,739. 


1,081,598—Dec. 16, 1913. 
J. FLACHSLAENDER, K. P. GraeLert and M. Burr, Germany. (Bayer.) 
Green sulfur dye. 

Leuco INDOPHENOL derived from peri diamino naphthalenes, (obtained by condensing 
NAPHTHALENE 1.8-diamin and dichlor 4-amino PHENOL or derivs. with PHOSGENE) in alc. soln. 
with or without copper comps., is refluxed with Na,S and S. Dark powds., diff. sol. conc. sulf. 
(GB), sol. in Na,S (G); GREEN sulfide vat dyes, fast to boiling and light. 


Note 1,081,599 and 600. 


1,081,599—Dec. 16. 1913. 
J. FLACHSLAENDER, K. P. GRAELERT and M. Burr, Germany. (Bayer.) 
Green coloring-matter containing sulfur. 

Leuco thio INDOPHENOL derived from peri diamino napthalene (obtained by condensing 
NAPHTHALENE 1.8-diamin and dichlor 4-amino PHENOL, or deriv. with CARBON BISULFID) is refluxed 
in alc. soln. with Na,S and §S and a little CuSO,. Dark powds, sol. in conc. sulf. (GB), in 
Na,S (G); GREEN sulfide vat dyes, fast to boiling and light. 


Addition to 1,081,598. 


1,081,600—Dec. 16, 1913. 
J. FLACHSLAENDER, K. P. GraELert and M. Burr, Germany. (Bayer.) 
Olive-green sulfur dye. 

Leuco INDOPHENOL, of the peri diamino naphthalene class, derived from NAPHTHALENE 
1.8-diamin and 4-amino PHENOL, quinone chlorimid or derivs., is refluxed in alc. soln. with Na,S 
and S, with or without CuSO, Dark powds., insol. in conc. sulf., sol. in Na,S (G); brown 
GREEN sulfide vat dyes, fast to boiling and light. 


Addition to 1,081,598 and -599. 


274 DIGEST OF PATENTS 


1,081,601—Dec. 16, 1913. 
J. FLACHSLAENDER, K. P. GraELert and M. Burr, Germany. (Bayer.) 
Catechu-brown sulfur dye. 


4.5-Dinitro PYRIMIDIN is heated at 200-250° with Na,S and S with or without CuS0O,, 
Other pyrimidin derivs. containing at least one nitro group and varying conditions claimed. 
Dark powds., diff. sol. conc. sulf. (YBr), sol. in Na,S(RBr); catechu Brown sulfide vat dyes, 
fast to light. 


1,081,602—Dec. 16, 1913. 
J. FLACHSLAENDER, K. P. Graryert and M. Burr, Germany. (Bayer.3 
Brown sulfur coloring-matters. 


Dinitro PHTHALOPERINONE or derivs. containing at least one nitro group, is heated at 200° 
with NaS and §. Dark powds., sol. in conc. sulf. (Br), sol. in Na,S (YBr-RBr); catechu 
BROWN sulfide vat dyes, fast to light. 


1,081,638—Dec. 16, 1913. Alfred THauss, Germany. (Bayer.) 
Bline sulfur dye. 


Leuco INDOPHENOL, obtained from DIPHENYLAMIN 2-carbo or other diarylamin ortho carbo 
acid and nitroso PHENOL or derivs., is dissolved in alk., heated with polysulfid till boiling point 
is 112-113°, then refluxed. Dark powds., sol. in conc. sulf. (B-G), in Na,S (B); BLueE sulfide 
vat dyes. 


1,083,110— Dec. 30, 1913. 
A. Luttrincuaus, H. v.Drespacu and E. Scuwarz, Germany. (Badische.) 
Blue ecoloring-matters containing sulfur. 


InpDoPHENOL from dimethyl 4-PHENYLENE DIAMIN and PHENOL, or dimethyl thionolin or other 
4-amino 4’-hydroxy diphenylamin or analogous bodies, is heated in alcohol with polysulfids, con- 
taining high percentage of sulfur. Dark powds., sol. conc. sulf. (B-V), insol. NaOH or Na,S, 
sol. in alk. (NH,),S solns. which give stains when spots are exposed to air on filter paper (B-V); 
fast green BLUE to violet BLUE hydrosulfite vat (Y) dyes. 


1,083,489—Jan. 6, 1914. Wilhelm HaunenkAMM, Germany. (Hoéchst.) 
Sulfur dyestuffs and process of making same. 


INDOPHENOL sulfo acids derived from 4-diamins is condensed with naphthylamin sulfo acids, 
and product oxidized with 4-amino phenol to form a quinoid deriv., then heated with alk. 
polysulfids with or without CuSO,, which when present gives greener tones. Dark powds., 
insol. in alc., diff. sol. conc. sulf. (Bt), when heated (dark B), sol. in Na,S to leuco dye which 
is pptd. by salt; BLUE to GREEN reducing sulfide vat dyes, fast to washing and light. 

Note 776,855. : 


1,093,259—Apr. 14, 1914. 
J. FLACHSLAENDER, K. P. Gragiert and M. Burr, Germany. (Bayer.) 


Green sulfur dye. 


Leuco INDOPHENOL from an alphyl perimidin and 2.6-dichlor 4-amino phenol or analogous 
comp., is boiled with alk. polysulfids, alcohol and CuSO,. Products contain copper, and are dark 
powds., sol. in alk. sulfids (G); creEN sulfide vat dyes. 


1,096,715—May 12, 1914. Heinrich Hermann, Germany. (Berlin.) 
Sulfurized dyes and process of making same. : 

4-Oxy DIPHENYLAMIN, or deriv. which does not contain a sulfo group and the 4’ position 
is free so that but one 4-oxy aryl group is capable of assuming the quinoid form, is heated with 
sulfur or polysulfids with or without aluminum chloride. Products are insol. in usual solvents, 
sol. in con. and fuming sulf. to intense colors; red Brown reducing sulfide vat or hydrosulfite 
vat (Y) dyes. 

Note 1,098,259. 


1,098,259—May 26, 1914. Heinrich Heimann, Germany. (Berlin.) 
Sulfurized dyes and process of making same. 

4-Oxy 4’-methyl pIPHENYLAMIN, or other 4-oxy diarylamin in which the 4’ position is 
occupied by alkyl, or derivs or thio comps., but containing no sulfo group, is boiled with 
polysulfids. Dark brown powds., diff sol. in usual solvents (YBr-RBr), sol. in conc. sulf. (B), 


GROUP XV.—SULFUR 275 


in fuming sulf. (V), unchanged by boric acid, decol. by Al powd.; red Brown to brown RED 
sulfide vat or hydrosulfite vat dyes, fast to washing and Cl. 
Addition to 1,096,715. 


1,098,260—May 26, 1914. Heinrich Hermann, Germany. (Berlin.) 
Sulfurized dyes and process of making same. 


4-Oxy 4/-methoxy thio DIPHENYLAMIN or other alkoxy deriv., containing no sulfo group, 
is boiled with polysulfids. Dark brown powds., diff. sol. in usual solvents, sol. conc. and fuming 
sulf. (B-V), unchanged by boric acid, decol. by Al.; red Brown reducing sulfide vat or hydro 
sulfite vat dyes. 

Addition to 1,096,715 and 1,098,259. 


1,089,039—June 2, 1914. Heinrich Hermann and Paul Vircx, Germany. (Berlin.) 
Sulfur dyes and precess of making same. 


4-Alkyl 4’-oxy DIPHENYLAMIN, or deriv., is heated with 1-NAPHTHYLAMIN, or other aromatic 
amin, in sulfur to 200—250°, melt dissolved in Na,S and pptd. by current of air. Black powds., 
insol. in usual solvents, sol. in conc. and fuming sulf. (Bk); Brown to BLACK reducing sulfide 
vat or hydrosulfite vat dyes, fast to washing and Cl. 

Note 1,098,260. 


1,100,877—June 23, 1914. 
Richard Herz and Wilhelm Frouneperc, Germany. (Cassella, N. Y.) 
Fast yellow sulfid dyestuffs. (Process claimed.) 


Diacetyl diamin cARBAZOLE or other acylated deriv., especially when containing halogen, is 
heated in sulfur with BENZIDIN to 180-250°. Yellow to orange powds., insol. in aq. and usual 
organic solvents, sol. in conc. sulf. (RBr-Br), in Na,S (OBr); yveLLow reducing sulfide vat or 
hydrosulfite vat dyes, fast to Cl. 


1,102,171—June 30, 1914. O. SCHARFENBERG and W. HERzBeERG, Germany. (Berlin.) 
Sulfurized dyes and process of making same. 


INDOPHENOL from PERIMIDIN and 4-amino PHENOL, or quinone chlorimid, is heated with 
Na,S and §$ in alcohol. Dark powds., insol. in usual solvents; GREEN to brown GREEN sulfide 
vat or hydrosulfite vat dyes. 


1,105,515—July 28, 1914. Heinrich Hermann, Germany. (Berlin.) 
Sulfurized dyes and process of making same. 

4’-Oxy phenyl 1-NAPHTHYLAMIN or Other 4’-hydroxy diaryl amin in which only one hydroxy 
group is capable of assuming the paraquinoid form, and without sulfo group, is heated in sul- 
fur to 220-240°. Products are insol. in usual organic solvents, but are sol. in anilin, pyridin, 
and conc. and fuming sulf. with intense color; BLUE, blue-cRAy to BLACK reducing sulfide vat 
or hydrosulfite vat (Y) dyes, fast to washing, Cl. 

Note 1,096,115. 


1,112,445—Oct. 6, 1914. 
K. P. Graevert, M. Burr and J. FLACHSLAENDER, Germany. (Synthetic.) 
Sulfur dyes. 


PHTHALOPERINONE, or deriv., is heated with polysulfid in presence of CuSO, to 200-220°. 
Dark powds. sol. in conc. sulf. (Br); Brown sulfide vat dyes, fast to light. 
Note 1,126,630 for disulfo deriv. 


1,113,766—Oct. 13, 1914. J. FLACHSLAENDER, Germany. (Bayer.) 
Green sulfur dye. 

Leuco INDOPHENOL, from mono ethyl 1-NAPHTHYLAMIN or other mono alkyl deriv. and 2.6- 
dichlor 4-amino PHENOL, are heated with polysulfids and CuSO, to 105°. Product contains 
copper from melt. Black powds., sol. in conc. sulf. (B); Green sulfide vat dyes. 


1,115,188—Oct. 27, 1914. A. HamsBurcer, Germany. (Bayer.) 
Vat dye. Dibenzoyl 5.5’-diamino 2.2/-dianthraquinonyl thio ether sulfid, or derivs. 


Benzoyl 5-amino 2-chlor ANTHRAQUINONE, or other chlor deriv., is heated to 130° in 5 parts 
anilin containing Na,S. Powds. diff. sol. in organic solvents, insol. acids and alks., sol. in 
conc. sulf. (GB, etc.); fast YELLOW, ORANGE to RED hydrosulfite vat dyes. 

Note 1,115,189. 


276 DIGEST OF PATENTS 


1,115,189—Oct. 27, 1914. A. HAMBURGER, Germany. (Bayer.) 
Vat dye. 2.2’-Dianthraquinonyl thio ether. 


2-Chlor ANTHRAQUINONE is heated to 200-220° in naphthalene soln., with Na,S. Yellow 
powd., insol. alk. and acids, diff. sol. in organic solvents, sol. in conc. sulf. (VR); fast YELLOW 
hydrosulfite vat (OR) dye. 

Note 1,115,188. 


1,126,630—Jan. 26, 1915. 
K. P. GrareLert, M. Burr and J. FLACHSLAENDER, Germany. (Bayer.) 
Brown sulfur dye. 


PHTHALOPERINONE 5.8-disulfo or deriv., is heated in sulfur melt containing copper to 
200-220°. Dark powds., sol. conc. sulf. (Br); BRown to red BROwN sulfide vat dyes, fast to 
light. 

Addition to 1,112,445. 


1,128,368—Feb. 16, 1915. 
Albrecht Scumipt, K. Turess and Ernst Bryk, Germany. (Hdchst.) 
Vat dyestuffs and process of making same. 


CHLORANIL and ANILIN or other arylamin is condensed to dichlor dianilin guinonE, which 
is boiled with Na,S in alcohol, or with a sulfhydrate or xanthogenate in alcohol. Products are 
insol. in most organic solvents, sol. in hot C,H,;NO, (Br-RBr), in conc. sulf. (R-VB-B); yellow 
BROWN, red BROWN to RED hydrosulfite vat dyes. 


1,128,371—Feb. 16, 1915. Albrecht Scumipt and Gustav Kroniein, Germany. (Hochst.) 
Sulfur dyestuffs and process of making same, 

INDOPHENOL sulfo, from nitroso PHENOL and CARBAZOLE or N-alkyl or sulfo deriv., is boiled 
in sulfur and Na,S mixture. Products are sol. in aq., in conc. sulf. (B), insol. in organic sol- 
vents, pptd. by acids or salt, or air; dark BLUE sulfide vat dyes, fast to Cl and light, and suit- 
able for dyeing in apparatus. 


1,129,574—Feb. 23, 10915. G. KatiscHER and D. Nissen, Germany. (Cassella, N. Y.) 
Vat dyes and process of making same. Composition not claimed. 

1-Amino 2-methyl ANTHRAQUINONE, 3 parts, is heated to 200—230° in 15 parts sulfur with 1 
part 1.4-PHENYLENE DIAMIN, or Other aromatic polyamin (or substances which like nitro or azo 
comps., yield polyamino products when reduced) and excess sulfur removed by Na,S. Color 
of dye varies with the amin used. Dark powds., sol. in conc. sulf. (Br-BrG), changed with 
paraformaldehyde to (GB); RED to vioLET vat (BrR-V) dyes, fast to washing, Cl, light. 

For specific claims see 1,129,575. 


1,129,575—Feb. 23, 1915. G. KariscHer and D. Nissen, Germany. (Cassella, N. Y.) 
Vat dyes and process of making same. Composition not claimed. 

t-Amino 2-methyl ANTHRAQUINONE, is heated with BENZIDIN in 3.5 parts sulfur at 210-240° 
and excess S removed by Na,S. Dark powd., sol. conc. sulf. (Br) changed with p-formaldehyde 
to (BG); a violet RED vat (R) dye. 

For general claims see 1,129,574. 


1,1382,922—Mar. 23, 1915. 
J. FLACHSLAENDER, K. P. GraELeRT and M. Burr, Germany. (Synthetic.) 
Sulfur colors. ; 
PERIMIDIN is heated in sulfur melt to 200—-250° with copper or copper compound. Dark 
powds., sol. in Na,S (Br-RBr), in conc. sulf. (Br); Brown sulfide vat dye, fast to light, boiling. 


1,140,745—May 25, 1915. Bernhard JarcxEeLt, Germany. (Synthetic.) 
Sulfur dye. 

Ethyl anin1n or other aromatic base, and BENZIDIN or derivs. are heated in sulfur to 170- 
180°, then slowly to 230-250°, dissolved in dil. NaOH and pptd. by acid. Yellow powds., 
insol. aq., sol. conc. sulf. (YBr); yELLOw sulfide vat dyes, fast to boiling and Cl. 


1,151,628—Aug. 31, 1915. Karl Turess, Germany. (Héchst.) — 
Vat dyestuffs and process of making same. 


3.6-Dichlor 2.5-dianilino QUINONE in various diluents (alcohol, water, pyridin) is heated in F 
autoclave with sulfur or thio-sulfate and body to bind halogen, such as sod. acetate. Olive — 


GROUP XV.—SULFUR oy 


gray to black powds., insol. in organic solvents, sol. conc. sulf. with characteristic colors; BLACK 
to Gray sulfide vat dyes. 


1,165,531—Dec. 28, 1015. Carl MuLLER and Wilhelm Sroper, Germany. (Badische.) 
Brown sulfur dyes. 

3.6-Dimethyl 2.7-diamino acripin, “Acridin Yellow,’ derived from FORMALDEHYDE and 3- 
TOLUYLENE DIAMIN leuco base, or other amino acridin, is heated in 3-4 parts sulfur at 220-330°, 
cooled, again heated with 7.5 parts Na,S to 270°, dissolved in aq. and pptd. by air. Products 
are insol. in aq. and in usual organic solvents, sol. conc. sulf. (Br) and in hot Na,S; fast 
BROWN sulfide vat dyes. . 


1,175,230—Mar. 14, 1916. Max Burr and Alfred Tuauss, Germany. (Synthetic.) 
Sulfur colors. 
Leuco INDOPHENOL from tetrahydro 1-NAPHTHYLAMIN and 4-amino PHENOL or deriv., are 


boiled with Na,S and sulfur in alcohol. Dark blue powds., sol. conc. sulf. (B), and in hot 
Na,S; BLUE sulfide vat dyes, fast to boiling. 


1,187,614—June 20, 1916. Carleton Erzis, New Jersey. (Ellis-Foster.) 
Process of making dyestuffs. 

DINITROPHENOL, or dinitro chlor benzene, with or without PHENOL, cresol, or homologs, is 
refluxed with calcium polysulfid soln., or with mixture of sulfur and slaked lime, or other alk. 
sulfide. Bruack or Brown sulfide vat dyes. Process for making calcium vat compound is de- 
scribed. 


1,199,697—Sept. 26, 1916. H. Hermann, Germany. (Berlin.) 
Dyes and proéess of making same. 

4-NITRANILIN azo ethyl 1I-NAPHTHYLAMIN or related comp., with or without BENZIDIN, 3- 
toluylene diamin, or other diamin, is heated in sulfur to 180-250° then dissolved in conc. Na,$S 
soln. and oxidized by air. Brown powds., insol. in usual organic solvents, sol. in conc. and 
fuming sulf. (RBr), not changed by Al, sol. in Na,S or hydrosulfite (YBr); yellow BRowN 
sulfide or hydrosulfite vat dyes, fast to washing and acid. 


1,209,580—Dec. 19, 1916. Wilhelm Herzperc and Oswald SCHARFENBERG, Germany. (Berlin.) 
Sulfur dyes. 

InNDOPHENOL, from dichlor 4-amino PHENOL and methyl PERIMIDIN, or derivs., is heated 
with alk. polysulfid in alcohol. Dark powds., insol. in usual solvents, sol. in Na,S (G), in alk. 
hydrosulfite (Br-Y); GREEN sulfide vat dyes. 


1,244,795—Oct. 30, 10917. Z. Suzuki, California. 
Process for the production of a dyestuff. 

Rice hulls are boiled in dil. alk., then heated with Na,S and S to 150-180°. To modify 
color, add to rice hulls also rice, millet or wheat bran or buckwheat hulls. Brown sulfide vat 
dyes. 

Near S. 706—‘‘Cachou de Laval.” 


1,244,796—Oct. 30, 1917. Z. Suzuki, California. 
Process for the production of a dyestuff. 
Topacco stems are heated with dil. alk., then with Na,S and S to boiling temp. till dry. 
Color modified by using rice or wheat straw with tobacco stems. Brown sulfide vat dyes. 
Near S. 706—‘‘Cachou de Laval.” 


1,247,475—Nov. 20, 1917. Edward Wray, England. (Claus.) 

Manufacture of new indophenolic compounds and of dyestufis therefrom. 
4-Nitroso PHENOL, or homologs, is condensed in conc. H,SO,, with cARBAZzOLE, N-acetic acid 

or its esters, and resulting indophenol or its leuco form heated with alk. polysulfids and CuSO, 

or fused with Na,S and S at 115°, diluted, oxidized by air, and pptd. by acid. Blue black powd., 

insol. in aq. or acids, sol. in conc. sulf. (YG), pptd. on diln. (B), sol. in Na,CO, (GB); BLUE 

sulfide or hydrosulfite vat dyes. : 
Near S. 748—‘‘Hydron Blue R.” Note 919,572, 956,348, and 931,508. 


278 DIGEST OF PATENTS 


1,251,368—Dec. 25, 1917. Heinrich Heimann, Germany. (Berlin.) 
Sulfur dyes and their manufacture. 

3-TOLUYLENE DIAMIN, or other diamin, nitroamin, or deriv., is mixed with amino azo BENZENE, 
or other amino azo derivs., and heated in sulfur melt to 230-260°. Products are insol. in usual 
organic solvents, diff. sol. conc. sulf.; brown GREEN to BROWN to ORANGE sulfide vat dyes, fast 
to washing and dil. acids. 

Note 1,251,369. 


1,251,369—Dec. 25, 1917. Heinrich Hermann, Germany. (Berlin.) 
Dyes and manufacture thereof. 
3-TOLUYLENE DIAMIN, or other diamin, together with 4-NITRANILIN azO I-NAPHTHYLAMIN, or 
other nitro amino comp. is heated in sulfur to 220-260°. Varying conditions alter shade of 
dye. Dark powds., insol. in usual organic solvents, and in conc. sulf., easily sol. in alk. sul- 
fides or hydrosulfites; brown GREEN to BROWN sulfide vat dyes, fast to washing, dil. acids. 
Addition to 1,251,368. 


1,261,394—Apr. 2, 1918. Michael Injinsxy, Germany. (Wedekind.) 
Vat dyestuffs and process for their formation. 

ANTHRAQUINONE 2.6-disulfo or other, is melted with sod. thiosulfate at 250-300° until sul- 
fur ceases to sublime. (See long list of examples with properties.) Products insol. in alk., 


Na,5, conc. sulf.; GREEN, BLACK, orange RED hydrosulfite’ vat dyes, fast to Cl, light, washing, 
scalding, etc. Claims emphasize absence of solvent or diluent liquid in process. 


1,265,836—May 14, 1918. Raymond Vuipat, France. 
Method for preparing blue coloring materials. 

4-Amino PHENOL, or amino cresols, are refluxed with com’l crEsou, or other, until soluble 
in alk. then heated further with powd. S until evolution of H,S ceases. Products are sol. in 
alk. sulfids and hydrosulfites; BLuE sulfide vat dyes, fast to acids, chlorin. 

Note 1,265,837. 


1,265,837—May 14, 1918. Raymond Vipat, France. 
Method for preparing direct-dyeing black coloring materials. (Product 
claimed.) - 
4-Amino PHENOL or amino cresol, is refluxed with mixture of sulfur powder and com’l crRE- 
sot or other organic compound to aid reaction, until H,S ceases to evolve. Products are insol. 
in aq., sol. in alk. sulfids and hydrosulfites; puacx sulfide vat dyes, fast to acids and Cl. 
Addition to 1,265,836. Differs from earlier patent only in adding sulfur at once to first melt. 


1,268,803—June 4, 1918. Oswald SILBERRAD, England. 
Sulfur dye. (Process claimed.) 


Trinitro TOLUENE oily residues, obtained from purification process, are gradually added to 
aq., Na,S and S at 1oo° and temp. raised to 240° for 4 hours. Brown sulfide vat dye. Res- 
idue, left after distilling alcohol from mother liquor and recrystallizing trinitrotoluene, consists 
of 2.2 and 3.4 dinitro and 2.3.4 and 2.4.6 trinitro toluenes. 


1,274,351—July 30, 1918. Carleton Exuis, New Jersey. (Ellis-Foster.) 
Naphthol dye and process of making same. (Product not claimed.) 

2-NAPHTHOL, Other naphthols, or mixtures with nitro or halogen aryl comps., are heated at 
160-180° in sulfur and Na,S o- their equivalents. Dark or Black, of different shades or tones, 
sulfide vat dyes. : 


1,279,807—Sept. 17, 1918. Carleton Exuis, New Jersey. (Ellis-Foster.) 
Dye and process of making same. (Product not claimed.) 

Dinitro PHENOL, dinitro chlor benzene, or other aromatic nitro or phenolic body, is oats 
with equivalent proportion of aq. alk. sulfid at less than 50-75 lbs. pressure at 130-160° until 
all nitro groups are reduced. Various sulfid materials may be used, especially calcium poly- 
sulfid. Product is substantially sulfur free, and can be dried without decomp. Btack sulfide 
vat dyes. . 


it 


GROUP XV.—SULFUR 279 


1,302,671—May 6, 1910. Oscar KNEcHT, Switzerland. (Sandoz.) 
Process for the production of blue sulfur dyes. (Product also claimed.) 


Leuco INDOPHENOLS such as phenyl 4-amino 4’-oxy DIPHENYLAMIN, together with 4-NITRAN- 
ILIN or other non-hydroxy 4-nitro amino comp. of benzene series, is heated to 120~-125° with 
alcohol and alk. polysulfids under 6-8 atmos. pressure, alcohol distilled off and diluted soln. 
pptd. by acetic acid or air. Blue powds., insol. in aq. or alc., sol. in conc. sulf., anilin and 
pyridin (B); BLueE sulfide vat dyes. 


1,808,552—July 1, 1919. Hajime NaGAsHIMA, Japan. (Tainan Seito.) 
Process of manufacturing sulfid dye from filter-cakes of sugar-juice. 


Filter cakes from juice of sugar cane containing lime for defecation, are powdered, mixed 
in paste, and treated by steam and sufficient acid (preferably HNO,) to decomp. lime comps., 
filt., residue washed, squeezed as dry as possible, mixed with powd. sulfur and NaOH, dried, 
powd. and heated to fusion, finally volatilizing excess S. Operation may be varied as shown. 
Brown sulfide vat dye (no claims). 


1,810,751—July 22, 19109. B. J. Hatvorsen and C. Horsyst, Norway. 
Manufacture of sulfur dyes. 


CymMoL, a byproduct from mfr. of sulfite cellulose, is oxidized by HNO, to 4-ToLutc acid, 
nitrated by mixed acid, and heated with polysulfids at 250.° By producing mono and dinitro 
comps. separately, desired shades can be produced more easily. Brown sulfide vat dyes. 


1,314,92S8—Sept. 2, 1919. Chester E. ANpREws, Pennsylvania. (Selden.) 
Sulfur dyes and process of making same. 


Nitrogen containing CYMENE deriv., such as 1-methyl 2-amino 4-isopropyl 5-amino BENZENE 
or other mono- or di-alkyl, acetyl, formyl, nitroso, nitro, hydroxy, or azo derivs., is heated in 
sulfur with 3-toluylene diamin or other aromatic nitrogen deriv. to 200—220° or temp. sufficient 
to form H,S, dissolved in hot Na,S soln. at 110° and pptd. by air. Vari-coLorEp (except red) 
sulfide vat dyes, more brilliant in shade than corresponding sulfur dyes from benzene derivs. 


1,314,929—Sept. 2, 1910. Chester E. AnpreEws, Pennsylvania. (Selden.) 
Green sulfur dye and process of making same. 


4-Amino PHENOL, homologs or derivs., with amino CYMENE, nitro CYMENE, or acetyl comps., 
etc., are melted in sulfur at 200-300°, with or without diluent such as glycerin, cresols, anthra- 
cene, naphthalene or analogous comps. until evolution of H,S ceases, powd., dissolved in dil. 
NaOH and pptd. by acid or bicarbonate. Brown black powds., diff. sal. aq., sol. alk. (G) and 
in Na,S (Br); fast GREEN sulfide vat dyes, more brilliant and faster than analogous comps. from 
anilin. 


1,316,742—Sept. 23, 19109. James S. Ropeson, New Jersey. 
Manufacture of dyestuffs. (Product claimed.) 


Sulfite cellulose waste liquor (lignosulfonates or com’l dried product) is treated with a sul- 
fate or oxalate, etc. of a metal such as Al, Fe, Zn, Cu, etc., that will form soluble lignosulfates, 
the pptd. lime salt removed, metal salt pptd. from soln. by NaCl or Na,SO,, etc., sepd., dried, 
and fused at low heat in Na,S and S. Different metals produce varying shades, and yield gray 
black powds., sol. in aq. Brown to BLAcK sulfide vat dyes. 


1,318,022—Oct. 7, 1919. Charles STaropinEetz, Florida. (Barkings, 1%.) 
Sulfur dye. (Process claimed.) 
Oily residue obtained in purification of trinitrotoluol by alcohol, containing various nitrated 


derivs., is gradually added to mixed Na,S and S melt and heated to 160°. Product is a BROWN 
sulfide vat dye. 


1,827,862—Jan. 13, 1920. Frank E. Coomss, California. 
Sulfite-waste-liquor preparation and process of making same. 


To sulfite cellulose waste liquor, with or without 1-2 per cent H,SO,, iron filings or wire 
are added, and, if desired, a little copper as accelerator, and reaction continued “‘to an extent 
sufficient to produce fargoing reduction of organic bodies present.”” Dyes of lighter shades are 
attained by using Zn, Sn, etc. With copper, reduction is best made electrolytically. Brown’ 
(khaki) sulfide vat dyes, that may be used on acid mordants. 


280 DIGEST OF PATENTS 


1,329,898—Feb. 3, 1920. I. A. F. Haas, France. (St; Denis.) 
Blue sulfur dye and process of manufacturing same. 


2.4.5-Trichlor nitrobenzene heated with ANILIN in presence of sod. acetate gives dichlor 
nitro DIPHENYLAMIN, which when condensed in H,SO, with 4-nitroso PHENOL and product re- 
duced gives 4’/-oxy phenyl 2.4-diamino 4.5-dichlor pDIPHENYLAMIN, which is heated in 4 parts 
sulfur at 200°, powd. dissolved in Na,S soln. and pptd. by air. Buue sulfide or hydrosulfite 
vat dye. 


1,3846,153—July 13, 1920. Alan I. Appripaum, New Jersey. (Import By-) 
Sulfur color and process of manufacturing the same from aloe resin. 

ALOE resin, obtained as a by-product after extraction of aloin from aloes, boiled with soln. 
of Na,S and S or heated under greater than atmospheric pressure at varying temps. to produce 
color desired, melt dissolved and pptd. by acid. A salt of a metal such as Cu, Fe, Zn, Ni, Co, 
Ce, etc., or mixtures thereof, or BENZIDIN, etc., may be added to melt to alter or brighten the 
color. VarI-coLoRED sulfide vat dyes. 

Note 1,346,154. 


1,346,154—July 13, 1920. Alan I. AppeitpAum, New Jersey. (Import By-) 
Salfur color and process of manufacturing the same from aloes. (Product 
not claimed.) 


Practically same claims as for 1,346,153, but including as material anoks both before and 
after extraction of aloin. Claims are made more general in every way. VArI-coLoRED sulfide 
vat dyes. 


1,358,490—Nov. 9, 1920. Max Wyter, England. (Levinstein.) 
Sulfur dyestuff. (Process, not product, claimed.) 


ACENAPHTHENE heated at 250-300° in 3.5 parts sulfur till sol. in Na,S, melt powd., dis- 
solved in ten per cent Na,S and pptd. by HCl. When heated in other proportions of sulfur two 
products are obtained—dinaphthalene thiophene and trinaphthalene benzene. Red Brown sul- 
fide vat dye. 


1,405,446—Feb. 7, 1922. J. ScumipLin and W. Brinner, Germany. 
Vat dyestufis and process of making same. 


Chloranil or other halogenated BENZOQUINONE, is condensed with 3-NITRANILIN or its sub- 
stitution products (nitro group always in meta position to amino) to CHLORANIL 3-nitranilid, 
which is heated in 25 parts aq. (NH,).S or other alk. sulfide at 120°. Color of product varies 
with nitroarylamin, with alk. sulfid used, and with temp. and duration of reaction. Dark powds., 
sol. in aq. and most organic solvents, sol. in conc. sulf. (V-B-GB); Brown to GrEEN hydrosulfite 
vat (Y-BrY) dyes. 


1,440,833—Jan. 2, xb23. 
Georg KatiscHER, Jens Mitituer and Detley Nissen, Germany. (Cassella.) 
Yellow vat dyestuff. (Process also claimed.) 


2-Methyl ANTHRAQUINONE, 2 mols., is heated above 200° in sulfur with 1 mol. of a para 
diamin or comp. yielding a para diamin, such as BENZIDIN, 4-PHENYLENE DIAMIN, 4-nitranilin, 
4-amino azo benzene, etc. and product purified by extraction with Na,S, conc. H,SO,, etc., then 
oxidized at 60—-100° with NaOCl soln. or other. Products are insol. in aq. and organic solvents, 
sol. in conc. H,SO, (Y-Br); GREEN to orange YELLOW reducing vat (GBr to Br) dyes, fast to 
washing, Cl and light. 


1,449,681—Mar. 27, 1923. Edwin Kramer and Ludwig Zen, Germany. (Bayer.) 
Sulphur dye. 

Benzyl methyl 1nDOPHENOL, obtained from benzyl methyl ANILIN and Quinones chlorimid or 
other, is refluxed 60 hours in alc. soln. with 4 parts of a polysulfid from tech. calcined Na,S 
and S (4:5). Dark blue powd., sol. conc. H,SO, (B); green sLug reducing vat (Y) dyes, fast 
to boiling, Cl and light. 


1,465,853—Aug. 21, 1923. William Lewcocx and Snow B. TaLLantyre, England. (Gas Coke.) 
Manufacture of condensation products from carbazole and p-nitroso phenol 
and its derivatives. 


4-Nitroso PHENOL in 23.5 parts 93 per cent H,SO, is cooled in a jacketed vessel to —20° 
by liq. NH, or other and about 1.4 parts 94.5 per cent CARBAZOLE added in small charges of 


. 
F. 
: 


GROUP XVI.—THIAZIN 281 


powd. solid, agitating well and keeping temp. constant at 20°. After maintaining temp. for 
further half hour, product is poured in fine stream into 30 vols. dil. aq. NH, at not above 15°. 
Temp. should not exceed —5° but the lower the temp. the higher the grade of product. Product 


on thionation gives BLUE sulfide vat dye. (Not claimed.) 


1,471,150—Oct. 16, 1923. Karol Dz1ewonsx1, Poland. 
Process for the preparation of dyestuffs. Acid and sulfur dyes from dinaphthalene 
thiophene. 


One part DINAPHTHALENE thiophene is heated at 1roo-110° for 8 hours with 4 parts conc. 
and o.2 parts fuming (20 per cent) sulf. acid. Much sO, is liberated and 3 compounds formed 
—a violet black and two red or brown sulfo derivs., w ich by treatment with CaCO, or BaCoO, 
are separated by different solubilities into orange RED and red Brown acid dyes aaa a grey 
VIOLET sulfide dye. 


1,471,854—Oct. 23, 1923. Walter A. Manss, Delaware. (du Pont.) 
Blue sulfur dye. (Process also claimed.) 


One part INDOPHENOL or leuco comp., derived from 4-nitroso PHENOL and DIPHENYLAMIN, 
is refluxed in aq. containing 2.5 parts cryst. Na,S and 1 part S for 40 hours at 115-120°, di- 
luted, pptd. by air and filt. One part of dried dye in 8 parts 93 per cent H,SO, and 1.3 parts 
aq. is heated at 80-85° till homogeneous (10 m), dild., filt. and dried. Treatment with sulfuric 
acid renders impurities soluble in Na,S to a clear vat. Variations of procedure are claimed. 
BuveE sulfide vat dye. 


Group XVI.—THIAZIN. 


204,796—June 11, 1878. Heinrich Caro, Germany. 
Improvement in the production of dye-stuffs from methyl-aniline. (Prod- 
uct, not process, claimed.) Tetra methyl diamino phen-thiazin. 

Dimethyl ANILIN and homologs, converted to nitroso compound with HCl and nitrite, re- 
duced to amino comp. with H,S and oxidized with FeCl, etc. Buug basic mordant dye that 
may be formed on fiber, suitable for printing. 

S. 650—‘‘Methylene Blue B.”’ Note 270,311 for method using ZnS and acid, and 323,514 
for method using Na,S and electrolysis. 


246,327—Aug. 30, 1881. Carl A. Martius, Germany. 
Methyl-blue color. (Process also claimed.) Tetra methyl diamino phen-thiazonium 
chloride. 

SuULFANILIC acid azo dimethyl aniLtn, or ‘‘Methyl Orange,’”’ heated to ros—r1o° in closed 
digester with excess NH,SH, filt., oxidized by FeCl,, then pptd. by ZnCl,. Sulfur and anilin 
sulfo acid are separated during reaction. Briur direct and basic mordant dye. 

Near S. 6590—‘‘Methylene Blue B.” (Caro.) 


270,311—Jan. 9, 1883. Eduard Hepp, Germany. (Oehler.) 
Manufacture of blue dye stuff or coloring matter. (Product also claimed.) Tetra 

methyl diamino phen-thiazin. 

Nitroso dimethyl AnILIN, or other, 1 ke is dissolved in conc. H,SO,, (1.40) and treated 
with ZnS at 20°, or other, then oxidized with FeCl,. Brug basic mordant dye. 

S. 659—“‘Methylene Blue.’”? Note 204,796 for eel patent and 323,514 for method using 
Na,S and electrolysis. 


282,836—Aug. 7, 1883. August Brerntusen, Germany. (Badische.) 
Manufacture of coloring-matters. (Product, not process, claimed.) Apparently an 

unsubstituted diamino phen-thiazin. 

Thio DIPHENYLAMIN, made according to 282,835 from diphenylamin and §, is nitrated, re- 
duced, and then oxidized. Vuio.et basic and basic mordant dye. 

This is a product patent for which 286,527 is the process. Note 282,835, among Intermedi- 
ates, for first part of process. 


286,527—Oct. 9, 1883. August Brerntusen, Germany. (Badische.) 
Process of obtaining coloring-matter or dye-stuff from thiodiphenylamine. 
Unsubstituted diamino phen-thiazin. 


282 DIGEST OF PATENTS 


Thio DIPHENYLAMIN is nitrated, reduced and oxidized. 
Note 282,836, which is the product patent for above and 282,835, among Intermediates, for 
mfr. of thio diphenylamin. 


323,514—Aug. 4, 1885. Wilhelm Mayert, Germany. (Berlin.) 
Manufacture of methylene-blue by electrolysis. Tetra methyl diamino phen-thi- 
azin. 


4-Amino dimethyl aniiin, derived from nitroso dimethyl anilin, or any primary, secondary 
or tertiary aromatic amin, or hydrazo compounds of same, in Na,S soln., is subjected to elec- 
trolysis. Biux basic mordant dye. 

S. 659—“‘Methylene Blue.” Note 204,796 for original patent and 270,311 for modification 
with ZnS. 


362,592—May 10, 1887. Eduard Utiricu, Germany. (Hdchst.) 

Trimethylethylthionin-blue coloring matter. Trimethyl ethyl thionin blue. 
4-Amino dimethyl ANILIN together with ethyl methyl ANILIN is oxidized with bichromate 

and H,SO,, in presence of hyposulfite, and color pptd. by ZnCl, and salt. Biuxr basic mordant 


dye, fast to washing. 
S. 661—‘“Thionin Blue GC.” Note 366,639. 


366,639—July 12, 1867. Eduard Utiricu, Germany. (Héchst.) 
Production of dimethyldiethylthionin-blue. (Process, not product, claimed.) Di- 
methyl diethyl] thionin blue. 

Dimethyl anizin in HCl soln. is converted to nitroso deriv. by HNO,, reduced by Zn to 
4-amino dimethyl ANILIN, excess HCl removed by Zn, product oxidized and condensed with di- 
ethyl ANILIN by boiling with hyposulfite and bichromate, SO, expelled by acid and leuco dye 
oxidized. Buus basic mordant dye, fast to washing. 

S. 659—‘‘Methylene Blue,” S. 661—‘‘Thionin Blue GC.” Note 362,592 and 366,640. 


366,640—July 12, 1887. Eduard Uuiricu, Germany. (Hdchst.) 
Production of diethylmethylthionin-blue. (Product, not process, claimed.) Diethyl 
methyl thionin blue. 

Diethyl ANILIN is converted to 4-amino diethyl ANILIN as in 366,639, then condensed and 
oxidized together with methyl ANILIN by bichromate in presence of hyposulfite. B1iuxr basic mor- 
dant dye, fast to washing. 

S. 659—‘‘Methylene Blue,” S. 661—‘“‘Thionin Blue GC.” 


368,716—Aug. 23, 1887. Edward Greprin, Switzerland. (Geigy.) 
Process for the production of blue coloring-matter. (Product, not process 

claimed.) as-Dimethyl diamino thionin or ‘“Gentianin.” 

4-Amino dimethyl aniLin, or other, together with 4-PHENYLENE DIAMIN, or other, is con- 
densed and oxidized in presence of H,S in acid soln. Biux basic mordant dyes. 

Near S. 661—‘‘Thionin Blue GO” Schulz, 1904 ed., 587. Note also Formanek, who pro- 
nounces this to be a mixture of Methylene Blue and Lauths Violet. (Zeit. Farb. u. Text Chem. 


1904.) 


384,480—June 12, 1888. Edward Uuiricu, Germany. (Héchst.) 
Production of blue coloring-matter. Improved method of mfr. for Methylene Blue. 
Amino dimethyl an1uin, derived from the nitroso comp. by reduction with Zn and HCl then 
free HCl removed by Zn, is mixed with 1 mol. dimethyl aniLin, hyposulfite and bichromate and 
heated. BuiuE basic mordant dye. 
S. 659—‘‘Methylene Blue.”’ 


416,055—Nov. 26, 1889. 
Gottlieb DANDLIKER and Heinrich A. BernrusEn, Germany. (Badische.) 
Manufacture of toluidine-blue. (Product also claimed.) Tetra methyl diamino di- 
methyl phen-thiazin. 

Dimethyl aniLIn treated with HNO,, to form nitroso dimethy) anizin, then reduced to 
para amino comp., is treated with thiosulfate and acid or acid salt, and bichromate to form thio- 
sulfo deriv. and this with 2-ToLuripIN and more bichromate forms INDAMIN, which is boiled with 
' ZnCl, soln. Brive basic mordant dye for printing. 

Note Schulz index,—Toluidin Blue, similar to Methylene Blue. 


GROUP XVI.—THIAZIN 283 


434,493—Aug. 19, 1890. Arthur WEINBERG, Germany. (Cassella.) 
Blue dye. Diethyl dibenzyl diamino phen-thiazin disulfo or other. 


Ethyl benzyl anixin sulfo acid or other, is treated as in usual methylene blue process. 
(Treat with nitrite in strong acid soln., reduce nitroso comp. thus formed in alk. soln. with 
Zn, oxidize the ethyl benzyl 4-phenylene diamin sulfo acid in presence of H.,S to an Indamin 
containing sulfur, then heat with ZnCl,.) Green BLuE acid dye. ; 

S. 662—“Thiocarmin R.”’ 


469,329—Feb. 23, 1892. Arthur WEINBERG, Germany. (Cassella.) 
Blue dye. Dimethy! diamino diortho toluthiazin, 

Methyl 2-ToLu1IpIN nitrosamin, or other, in strong acid soln. is reduced at O° with Zn., 
neut. and sod. thiosulfate then bichromate added. Methyl 2-ro_urpin, is further added and 


heated with ZnCl, and bichromate. Buiug basic mordant dye. 
S. 663—‘‘New Methylene Blue N.” 


522,897—July 10, 1894. Wilhelm Herrzperc and Oscar Weser, Germany. (Berlin.) 
Blue dye. (Process also claimed.) Dimethyl 4’-amino phen 3.4-dioxy 7-sulfo 1.2-naphth thi- 
azin. 


Dimethyl 4-PHENYLENE DIAMIN, or any alkyl comp. of same, is condensed in aq. with 1.2- 
NAPHTHOQUINONE 3.6-disulfo or other, then added to fuming H,SO, and S$ or substance that 
will form sulfur sesquioxide (S,O,), and finally heated to 90°. Buiuxr acid mordant (Cr or other 
metal) fast dyes, suitable for printing and for lakes. 

Near S. 667—‘“‘Brilliant Alizarin Blue.” Is this patent a duplication of S. 667? 


524,322—Aug. 14, 1894. Bernhard Heymann, Germany. (Bayer.) 
Blue dye. (Process also claimed.) Dimethyl 4’-amino phen 3.4-dioxy 7-sulfo 2-naphthiazin, 

Na salt, or derivs. 

Nitroso dimethyl aANILIN is dissolved in dil. acetic acid (33 per cent), thiosulfate added and 
temp. raised to 80°, then 1.2-NAPHTHOQUINONE 6-sulfo mixed therewith at same temp. Other 
components claimed. Buiur acid mordant dye fast to light, milling. 

Near S. 666—‘“Indochromogen S. or 667 “Brill. Alizarin Blue G.”? Note 524,323. 


§24,323—<Aug. 14, 18094. Bernhard HrymMann, Germany. (Bayer.) 
Blue dye. (Process also claimed.) Methyl 4”-sulfo benzyl 4’-amino phen 3.4-naphtho quinone 
1.2-thiazin. 
4-Nitroso methyl 4’-sulfo benzyl aniu1INn, or other, dissolved in aq. containing sod. acetate 
and acetic acid, is heated to 80°, thiosulfate added then 1.2-NAPHTHOQUINONE 4-sulfo, or 1I- 
nitroso 2-naphthol, or nitroso 1-naphthol 4-sulfo. Brug acid mordant (Cr) dyes, fast to light 
and milling. 


538,183—Apr. 23, 1895. Jakob ScuMip and Johannes MoHLER, Switzerland. (Basle.) 
Blue dye. (Process also claimed.) Methyl 4”-sulfo benzyl 4’-amino phen 3.4.7-trioxy 1.2- 
napthiazin. ; 


Methyl 4’-sulfo benzyl aniL1N is converted to nitroso deriv. by nitrite and HCl, heated to 
80-100° in 40 per cent acetic acid with thiosulfate to form 4-amino methyl 4’-thio sulfo benzyl 
ANILIN, which is heated with 1.2-NAPHTHOQUINONE 7-oxy 4-Sulfo. Brux acid mordant (Cr) dye 
fast to light. 

Near S. 667—‘“Brill. Alizarin Blue.’’ Note 560,795 for similar dye. 


539,738—May 21, 1895. Wilhelm Herzperc and Oscar WEsER, Germany. (Berlin.) 
Blue dye. (Process also claimed.) Dimethyl 4’-amino phen 4-amino 3-oxy 7-sulfo 1.2-naph- 
thiazin. 


I-AMINO 2-NAPHTHOL 6-sulfo, is condensed with nitroso dimethyl aniuin by dissolving in 
aq., and dried product heated at 40-60° in fuming sulf. (25 per cent SO,) containing sulfur or 
$,0,, etc. Other components claimed. Buve acid mordant dye suitable for lakes for printing. 

The dye of 522,897 contains the quinone group while above has quinonimid instead. 


560,795—May 26, 1806. Bernhard Heymann, Germany. (Bayer.) 
Blue dye. (Process also claimed.) Methyl 4”-sulfo benzyl 4’-amino phen 3.4-dioxy 7-sulfo 
naphthiazin. 


19 


284 DIGEST OF PATENTS 


4-Nitroso methyl 4’-sulfo benzyl ANILIN in hot 33 per cent acetic containing sod. acetate is 
poured into boiling soln. of thiosulfate, cooled to 60°, and mixed with 1-nitroso 2-NAPHTHOL 
6- or 7-sulfo or 1.2-naphthoquinone 6-or 7-sulfo, or other. Buug acid mordant (Cr) dyes, fast 
to light, milling, used also for printing. 

Near S. 667—“‘Brill. Alizarin Blue.’”? Note 538,183 for similar dye. 


606,212—June 28, 1808. Bernhard Heymann, New York. (Elberfeld.) 
Blue dye and process of making same. 4’-Dimethyl amino phen 3.4.7-trioxy 1.2-naph- 

thiazin 7-acetic acid. 

4-Nitroso dimethyl ANILIN is boiled with bisulfite to form 4-amino dimethyl Aanizin thiosulfo 
acid, then condensed with 1-nitroso 2.7-dioxy NAPHTHALENE 7-acetic acid. Brius acid mordant 
dye, fast to light and milling. 

Near S. 667—‘‘Brilliant Alizarin Blue G.”’ 


607,408—July 12, 1896. _ Emil Eusarsser, Germany. (Dahl.) 
Blue dye for wool. (Process also claimed.) Constitution not indicated. 


4-nitroso dimethyl ANILIN is heated in 30 per cent acetic acid with bisulfite to form 4- 
amino dimethyl aninin thiosulfo which is condensed with 2-dinaphthyl 3-PHENYLENE DIAMIN 
disulfo and oxidized with bichromate. The two operations can be carried on at the same time. 
BLUE acid dye. 

S. 665—‘‘Urania Blue.” 


Group XVII—THIOBENZENYL. 


406.952—July 16, 1889. William Prirzincer, Germany. (Bayer.) 
Thioparatoluidine. Thio 4-toluidin sulfo. 


4-TOLUIDIN, 2 mols., is melted with 2 mols. sulfur at 180-200° till H,S ceases to evolve, 
then at 250° to form 2-thio 4-TOLUIDIN. YELLOW direct and developed (coupled) dye that can 
be coupled on fiber. ; 

S. 616—“Primulin.”? Note original pat. by Green, and also 415,359. 


412,97S8—Oct. 15, 1889. Joseph RosENHEK, Germany. (Cassella.) 
Production of yellow dye-stuffs. Trimethylated dehydro-thio-4-toluidin. 


Thio base of 4-TOLUIDIN, or other, derived by heating with sulfur, is heated with METHYL 
alcohol, benzyl chloride or other, and acid in autoclave to 160-170°. Green-yELLow (fluores- 
cent) basic mordant dye, used for printing. 

S. 618—‘‘Thioflavin T.’’ 


412,979—Oct. 15, 1880. Joseph RosENHEK, Germany. (Cassella.) 
Production of yellow coloring-matters. <A sulfonated Thioflavine T. (S. 618.) 
Alkylated base of thio toLurpIN or xylidin obtained as in 412,978 (crude or purified) is 


sulfonated. YELLOw, green fluorescent basic dye. 
S. 615—“Thioflavin S.” 


415,359—Nov. 19, 1880. Emil Exsarsser, Germany. (Dahl.) 
Process of making paratoluidine sulpho-acid. Mono sulfo dehydro thio 4-tolu- 
idin deriv. ; “ 


4-TOLUIDIN is melted with sulfur to form dithio 4-roLurpINn, purified by treatment with al- 
cohol (removes about 30 per cent) and sulfonated. YxELLow direct dye that can be diazotized § 
on fiber and coupled to form various colors. é 
S. 616—“Primulin.” Practically a method of purification only, otherwise it appears to be 


a duplication. 


440,281—Nov. 11, 1890. Christopher Ris, Switzerland. (Geigy.) 


Yellow dye. 

PoLycHROMIN (sulfo acid of thio 4-ToLUIDIN or PRIMULIN) is diazotized, excess ammonia 
added, allowed to stand 12 hours, then boiled. Nitrogen is given off. Product can be diaz- 
otized again but requires one-half quantity nitrite. A yELLow direct dye. 


GROUP XVIII.—TRIPHENYLMETHANE 285 


446,009—Feb. 10, 1801. William Prirzincer, Germany. (Bayer.) 
Yellow dye. 
a) Dehydro thio 4-rotuip1n sulfo or Primulin is coupled with second mol. of same in acetic 


or alk. soln. b) Dye results also from boiling diazo thio 4-roLuipin sulfo with NH,. Green- 
YELLOW direct dye. 


S. 198—“‘Clayton Yellow.’’ Note 406,952. 
Group XVIII.—TRIPHENYLMETHANE. 


32,965—July 30, 1861. George E. C. peLarre, France. 


Improvement in aniline colors. Triphenyl triamino triphenyl methane or triphenyl 
para rosanilin. 


RosANILIN, or other, heated to 165° with ANILIN, water and acid added and further heated. 
BLuE and vioLET basic dyes. 


Near S. 520—‘‘Spirit Blue.’’ 


43,066—June 7, 1864. August W. Hormann, England. 


Improvement in preparing coloring-matters for dyeing and printing.  Tri- 
ethyl triamino diphenyl tolyl methane. 


ROSANILIN and ETHYL bromide, iodide or other, heated with methyl alcohol in closed vessel 
under pressure to 212°. BLvueE or vioLerT basic dyes, suitable for printing. 


S. 514—“Hofmann’s Violet.” 


50,335—Oct. 10, 1865. Charles CLiEmMM, Pennsylvania, and August CLemm, Germany. 
Improvement in the manufacture of aniline-red. 

ANILIN sulfate is fused with equal weight sodium arsenate in iron vessel at 210°. Rexp 
basic mordant dye. 

S. 512—‘‘Fuchsin.” 


53,241—Mar. 13, 1866. Philibert CHEVALIER, France. 
Improvement in the manufacture of coloring matters from aniline. (Prod- 

ucts also claimed.) Composition not stated. 

ANILIN as arsenate mixed with KNO, heated at boiling temp. Rep and vioLer basic mor- 
dant dyes, different from Fuchiacine and “‘vioLET”’ previously known. 

Near S. 512—‘“‘Fuchsin.”’ 


204,797—June 11, 1878. Heinrich Caro, Germany. 
Improvement in methyl-aniline violet colors. Trisulfonated Methyl Violet, or 
other. 


MeEtHyYL vi0oLET, Hofmanns’ Violet, or other, sulfonated by fuming sulfuric acid between 
1oo and 120°. VuoLEt acid mordant (Al, Sn, etc.) dyes. 

S. 525—“‘Red Violet 3RS,” and S. 526—‘“‘Acid Violet 4RS.” Note addition patent 204,798 
for alkyl homologs. 


204,798—June 11, 1878. Heinrich Caro, Germany. 
Improvement in ethyl-rosaniline dye-stuffs. Trisulfo acids of ethyl rosanilin. 


Sulfo acid of RosANILIN boiled with ErHyL iodide or other, in 50 per cent alcohol containing 
alkali. Vuioirer acid mordant (Al, Sn.) dye. ; 

S. s2s—‘Red Violet 5RS” and S. 526—‘‘Acid Violet 4RS.” Description of patent in 
Schulz does not give alkylation process. Addition to 204,797. 


222,257—Dec. 2, 1879. Oscar G. DorsNner, Germany. 
Improvement in green coloring matters. Tetramethyl diamino triphenyl carbinol. 


Brnzo trichloride, 2 parts, is heated to 110° with 3 parts dimethyl ANILIN in presence of 
metallic chlorides (Zn, Cd, Sn, Cu, Hg, Fe, etc.). GREEN basic dyes. 


S. 495—‘‘Malachite Green.” 


286 DIGEST OF PATENTS 


248,153—Oct. 11, 1881. Otto Fiscurer, Germany. 
Pr-vess of preparing leuco-base of aniline blue. Leuco base of anilin blue. 


4-Nitro BENZALDEHYDE is reduced in alc. soln. by Zn and HCl and resulting 4-amino BENz- 
ALDEHYDE is heated to 120-140° with DIPHENYLAMIN, methyl DIPHENYLAMIN and ZnCl,. BLuE 
basic dye. 

S. 521—‘‘Anilin Blue.’’ 


248,154—Oct. 11, 1881. Otte FiscHer, Germany. 
Process of preparing coloring-matter. Mixture of rosanilin and p-rosanilin. 


4-Amino BENZALDEHYDE derived from nitro comp. by reduction in ale. HCl and Sn, heated 
to 120-140° with 2 mols. anizuiIn HCl (containing toluidin) and ZnCl,, and oxidized. Rep basic 
mordant dye. 

S. 512—‘‘Fuchsin.”’ 


250,201—Nov. 29, 1881. Heinrich Caro, Germany. (Badische.) 
Sulfonated compound of rosanilin. (Process also claimed.) Rosanilin trisulfo. 


Fucusin is sulfonated at 120-170° with anhydrous acid. Rep acid dye. 
S. 524—‘“Fuchsin S$.” Note 250,247 for closely similar method and product. 


250,247—Nov. 29, 1881. } John Houiipay, N. Y. (Holliday.) 
Manufacture ef rosanilin colors. Rosanilin trisulfo (probably). 


RosANILIN is sulfonated in fuming sulfuric acid (69—-70°) at ordinary temp. Rep acid dye. 
S. 634—‘‘Fuchsin §.” Note 250,301. 


252,202—Jan. 10, 1882. Otto FiscHEer, Germany. 
Rosanilin-red coloring-matter. Mixture of rosanilin and para rosanilin. 


4-Nitro BENZALDEHYDE is condensed in presence of ZnCl, with aniL1n oil (comm’l) contain- 
ing toluidin and xylidin, reduced to leuco base then oxidized to rosanilin. REp basic mordant 
dye. 

S. 512—‘‘Fuchsin.” Original patent used commercial anilin and nitrobenzene with ZnCl, 
and Fe. 


252,203 


Preparation of rosanilin-blue coloring matter. Diphenyl para rosanilin. 


Jan.) 16, P2882. Otto Fiscuer, Germany. 


4-Nitro BENZALDEHYDE is condensed in presence of ZnCl, with DIPHENYLAMIN to form nitro 
leuco base, reduced then oxidized, and possibly sulfonated to form water sol. deriv. Buur basic 
dye. 

Near S. 520—‘‘Diphenylamin Blue.”? Addition to 252,202. 


262,680—Aug. 15, 1882. Friedrich Mann, N. Y. (Schoellkopf.) 
Manufacture of rosanilin color. Probably sulfonated rosanilin. 


ROSANILIN, or its salt, is dried at 100° and with 2 to 3 parts of carbyl sulfate or ETHIONIC 
acid is heated at 100° until test is not pptd. by alkali. Rep acid and acid mordant dyes. 
S. 524—“Fuchsin §.” 


263,420—Aug. 29, 1882. Raphael MeEnpoia, England. 
Manufacture of blue-coloring matters. 


2-NAPHTHYLAMIN sulfo, or other, coupled with dimethyl aniL1Nn, or other, is reduced with 
_ yellow (NH,),S, with possibly also some Zn dust, made acid, the pptd. sulfur and 2-naphthyl- 
amin sulfo acid filtered off, (later this is recovered) and soln. oxidized by FeCl,. Color is pptd. 
by ZnCl, and salt, and may be purified by reprecipitation. Biur basic and basic mordant dyes. 


266,912—Oct. 31, 1882. James H. Srespins, Jr., New York. 


Coloring-matter or dye-stufft. sym-Dimethyl diphenyl diamino triphenylmethane and — 


sulfo acids. 

Benzoyy chloride with 2 parts methyl DIPHENYLAMIN is heated with ZnCl, at 100°, cooled 
mass washed with aq. and converted to soluble sulfo deriv. by heating to 100-110° in fuming 
sulfuric, or pptd. as base from alc. soln. by KOH. GrEEN basic mordant dye. 

Near S. s04—‘‘Light Green S. F. bluish.” 


eS ee a 


Pd 


GROUP XVIII.—TRIPHENYLMETHANE 287 


283,766—Aug. 28, 1883. Eugen Fiscuer, Germany. (Hoéchst.) 
Manufacture of the nitro-leuco base of rosanilin. (Product, not process, claimed.) 
4-Nitro BENZYLIDIN chloride in ligroin, or other solvent, is heated on water bath with ANILIN 
(comm’l). By reducing agents product is converted into leuco rosanilin base. YELLOW to RED 
basic mordant dyes. 
S. 512—‘‘Fuchsin.” 


290,856—Dec. 25, 1883. Heinrich Caro, Germany, and Alfred Kern, Switzerland. (Badische.) 
Manufacture of dye-stuff. New method for making crystallized hexa methyl para ros- 

anilin. 

PHOSGENE is condensed with dimethyl anrLin in presen ; of anhyd. AICI,. Vuong? basic 
mordant dye. 

S. 516—“Crystal Violet.” 


290,891—Dec. 25, 1883. Alfred Kern, Switzerland. (Badische.) 
Manufacture of dye-stuff or coloring-matter. Hexamethyl para rosanilin. 


Dimethyl ANILIN is converted into tetra methyl diamino BENZOPHENONE, reduced to BENZ- 
HYDROL, condensed with dimethyl aniuin, then oxidized. VuioLEer basic mordant dye. 
S. 516—‘“‘Crystal Violet.” For processes, see 290,892. 


290,8982—Dec. 25, 1883. Alfred Kern, Switzerland. (Badische.) 
Manufacture of purple dye-stuff. New method for mfr. of hexamethyl para ros- 
anilin. 


Dimethyl ANILIN is converted into tetramethyl diamino BENZOPHENONE, reduced to benz- 
hydrol, condensed with dimethyl anitin then oxidized. VuroLer basic and basic mordant dyes. 
S. 516—‘‘Crystal Violet.’”’ Process for 290,891. 


290,893—Dec. 25, 1883. Alfred Kern, Switzerland. (Badische.) 


Manufacture of dye-stuff or coloring matter. (Product, not process, claimed.) 
Hexaethyl para rosanilin. 


Diethyl ANILIN is converted to tetra ethyl diamino BENZOPHENONE, reduced then condensed 
with diethyl ANILIN, finally oxidized. Vuioter (bluer than Methyl or Hofmann’s vioLEr) basic 
mordant dyes. 

S. 518—‘“‘Ethyl Violet.’”? Addition to 290,891. 


297,413—Apr. 22, 1884. Alfred Kern, Switzerland. (Badische.) 


Manufacture of ethyl-blue coloring-matter. (Product, not process, claimed.) 
Tetra ethyl phenyl naphthrosanilin. 


Tetra ethyl diamino BENZOPHENONE is condensed with phenyl 1-NAPHTHYLAMIN using POCI. 
BLuE basic mordant dye. 
Homolog of S. 559—‘“‘Victoria Blue B.”’ Addition to 297,414. 


297,414—Apr. 22, 1884. Alfred Kern, Switzerland. (Badische.) 
Methyl-blue coloring matter. Tetra methyl phenyl naphthrosanilin. 


Tetra methyl diamino BENZOPHENONE is condensed with phenyl 1-NAPHTHYLAMIN by means 
of POCI, Buuz basic or basic mordant dye. 
S. 559—‘“Victoria Blue B.” Note 297,413. 


297,415—Apr. 22, 1884. Alfred Kern, Switzerland. (Badische.) 
Methyl-blue coloring matter. Tetra methyl dibenzyl para rosanilin. 


Tetra methyl diamino BENZOPHENONE is condensed with dibenzyl an1L1n by means of POC. 
Blue-vioLet basic mordant dye. 
Near S. 517—‘‘Benzyl Violet.” Note 297,416 for addition. 


297,416—Apr. 22, 1884. Alfred Kern, Switzerland. (Badische.) 
Ethyl-blue coloring-matter. Tetra ethyl dibenzyl para rosanilin. 


Tetra ethyl diamino BENZOPHENONE condensed with dibenzyl aNILIN by means of POCI,. 
BLUE or VIOLET basic or basic mordant dyes. 
Near S. 517—‘‘Benzyl Violet.’”’ Addition to 297,415. 


288 DIGEST OF PATENTS 


307,401—Oct. 28, 1884. Charles Lows, England. 


Coloring-matter derived from aurin. (Process, not product, claimed.) Constitution 
not claimed. 


AvRIN is heated with ammonia and BENzorc acid or other organic acid then sulfonated de- 
riv. formed by either of two processes given. Rep oil sol. dye. 
Near S. 566—‘‘Red Corallin.” Process for 316,471. 


308,748—Dec. 2, 1884. Heinrich Caro and Alfred kern, Germany. (Badische.) 


Manufacture of purple-blue coloring-matter. (Product, not process, claimed.) 
Penta methyl naphthyl para rosanilin. 


Tetra methyl diamino BENZOPHENONE is condensed with methyl phenyl 1-NAPHTHYLAMIN by 
means of POCI,. BLuxE or vioLEt basic mordant dyes. 
S. 522—‘Victoria Blue 4R.” 


808,912—Dec. 9, 1884. Fritz MAcCHENHAUER, England. 
Manufacture of rosanilin derivatives. Constitution not claimed. 


“Azuline” (triphenyl para rosanilin hydrochloride from aurin and anilin) is sulfonated, 
then treated with nitric or nitrous acids. YELLOw acid dye. 


3810,128—Dec. 30, 1884. Emil ERLENMEYER, Germany. 
Production of rosanilin coloring-matters. 

Dimethyl ANILIN, or other tertiary amin, anilin or rosanilin, ANILIN, diphenylamin or other 
primary aromatic amin and NITROBENZENE or other oxidizing agent, are heated with iron filings, 
or other, to 180°. Rep basic mordant dyes. 

S. 512—‘‘Fuchsin.”? Apparently this is similar to Coupier’s original nitrobenzol process. 


316,471—Apr. 28, 1885. ‘ Charles Lowr, England. 
Manufacture of derivatives of aurin. (Product, not process, claimed.) Called “Rose 
Phenolin” and is probably substituted Red Corallin or Aurin R. 


AvrRin in alc. NH, soln. or other, is heated in open or closed vessel with BENzoIc or other 
organic acid. Rep basic dye. 


Near S. 556—‘“‘Red Corallin.’? Schultz credits this dye to Marnas, (no date). Note 307,- 
401 for process. 


318,484—May 26, 1885. Charles Lows, England. 


Manufacture of the derivatives of aurin. (Product, not process, claimed.) Sulfo- 
nated form of S. 556. 


AURIN is sulfonated and treated with ammonia. Rep acid or direct dye. 
S. 556—‘‘Red Corallin” sulf. Note 307,401 and 316,471. 


319,646—June 9, 1885. Leo Vicnon, France. 
Process of obtaining coloring-matter from amidoazo-benzole and homo- 
lozgues. 


Amino azo BENZENE is reduced by usual methods to 2 bases that are oxidized by bichromate, 
FeCl, or KMn0O,, etc. ViIoLET to BLUE to BLACK basic mordant dyes. 


325,827—Sept. 8, 1885. Friedrich FiscHrr, Germany. (Bayer.) 
Manufacture of violet dye-stuffs. Hexa ethyl para rosanilin by another process. 


Diethyl aNILIN is mixed with perchlor METHYL mercaptan (from chlorine and CS,) CaCO, 
added to neutralize acid and temp. raised to 110° till fused. VuioL_EtT basic mordant dye. 


Probably S. 518—‘‘Ethyl Violet.”’ For process, see 325,828 and 320,637. 


325,828—Sept. 8, 1885. Friedrich Fiscuer, Germany. (Bayer.) 
Violet methyl dye-stuff. Hexamethyl para rosanilin. | 


Dimethyl ANILIN is mixed then fused with perchlor METHYL mercaptan (from chlorine and 
CS,) using CaCO, to neut. acidity of melt. VioLter basic mordant dye. 


Probably S. 515—‘‘Methyl Violet.”” Note 325,827 for process. 


sie 


GROUP XVIII.—TRIPHENYLMETHANE 289 


327,953—Oct. 6, 1885. Alfred Kern and Carl L. Miutuer, Germany. (Badische.) 
Production of blue dye stuffs. Trimethyl triphenyl para rosanilin. 
PHOSGENE in form of vapor is passed into methyl prPHENYLAMIN which is kept at 100°, 


ZnCl, then added and more COCI, passed in. Buux basic dye. 
Near S. 520—‘“‘Diphenylamin Blue.” 


329,636—Nov. 3, 1885. Friedrich Fiscuser, Germany. 


Production of new violet dye-stuffs. Claims “new” dye but product probably is hexa 
methyl para rosanilin. 


Perchlor METHYL mercaptan (by action of Cl on CS,) run slowly into mixture of 3 mols. 
dimethyl aninin and CaCO, while cooling, then heated at 50-80° until molten and separated 
as acid salt. Vu1oLer basic and basic mordant dyes. 

S. 516—‘‘Crystal Violet.” 


329,637—Nov. 3, 1885. Friedrich Fiscurer, Germany. 
Violet coloring-matter. MHexaethyl para rosanilin. 
Perchlor METHYL mercaptan and diethyl ANILIN are heated to 100-110° with superheated 


steam. VIOLET basic mordant dye. 
Probably S. 518—‘“Ethyl Violet.’’ For process see 325,827. 


331,964—Dec. 8, 1885. Hugo HassENcAMp, Germany. 


Manufacture of benzylated methyl violet. (Product, not process, claimed.) Penta 
methyl sulfo benzyl para rosanilin disulfo. 


METHYL VIOLET is reduced with Zn in acetic acid soln., pptd. by alkali, purified, heated to 
130° under pressure in alkaline soln. with BENzyL chloride, the leuco base sulfonated then ox- 
idized. Buiur and vio.ier acid and acid mordant dyes. 

S. 527—‘‘Acid Violet 4BN.’’ For process, see 331,965. 


331,965—Dec. 8, 1885. Hugo Hassencamp, Germany. 
Manufacture of benzylated acid violet. Penta methyl sulfo benzyl pararosanilin 
disulfo. 
METHYL VIOLET is reduced, condensed with BENZyL chloride and sulfonated. VuioLet acid 
dye. 
S. 527—“‘Acid Violet 4BN.”’ See 331,964 for full process. 
333,649—Jan. 5, 1886. Charles Lowr, England. 


Manufacture of derivatives of aurin. Probably a mixture of para-rosanilin and aurin 
sulfo acids with intermediate products. 
AuRIN is heated at 38-100° in 5 parts conc. sulfuric to form sulfo acid, separated and 
heated in alc. or other soln. with NH, in open or closed vessels. Rep acid dye. 
Near S. 556—‘‘Red Corallin.” 


333,861—Jan. 5, 1886. Alfred Kern, Germany. (Badische.) 
Manufacture of soluble methyl-blue from rosanilin. (Product, not process, 
claimed.) ‘Methyl Blue B” or sulfonated triphenyl trimethyl rosanilin. 
Methyl pIPHENYLAMIN is heated to 100°, PHOSGENE gas added in presence of ZnCl, excess 
amin removed and color base dissolved in fuming sulf. (24 per cent SO,) below 5°, then gently 
heated at 60° till aq. sol. Buux acid and acid mordant dye. 


Near S. 337—‘‘Methyl Blue.” 


346,022—July 20, 1886. Henry Butt and Carl L. Miuurr, Germany. (Badische.) 
Sulphonated purple dye-stuff from benzyldiphenylamin. Tetra methyl phenyl 
benzyl triamino triphenyl carbinol sulfo acids. 

Tetra methyl diamino BENZOPHENONE is mixed with equal weight of benzyl DIPHENYLAMIN, 
POCI, and toluol added and heated to 80° then at 100-115°. The purified product is dissolved 
in 5 parts cold sulfuric (98 per cent) then heated at 100°, or fuming sulfuric acid below 10° 
may be used. Blue vio.er acid dye. 

Near S. 531—‘“Eriocyanin A.” Differences between product and blue dye 297,415 (Kern)’ 
are given. 


290 DIGEST OF PATENTS 


353,264—Nov. 23, 1886. Carl L. Miiiuer, Germany. (Badische.) 
Manufacture of sulphonated purple dye-stufis from basic rosanilin. Tetra 
ethyl methyl sulfo phenyl para rosanilin. 


Tetra ethyl diamino BENZOPHENONE is condensed with methyl DIPHENYLAMIN in presence of 
a little toluol and POCI,, then sulfonated. Blue vioLET basic dye. 
S. 532—‘‘Alkali Violet 6B.” 


353,265—Nov. 23, 1886. Carl L. Mituer, Germany. (Badische.) 
Manufacture of sulphonated purple dyestuffs from basic rosanilin. (Product, 
not process, claimed.) Tetra ethyl benzyl phenyl para-rosanilin sulfo. 


Tetra ethyl diamino BENZOPHENONE is condensed with benzyl DIPHENYLAMIN using a ‘little 
toluol and POCI,, then sulfonated. Blue vioret acid dye. 
Near S. 532—‘‘Alkali Violet 6B.”’ Addition to 353,264. 


353,266—Nov. 23, 1886. Carl L. Mittuer, Germany. (Badische.) 
Manufacture of sulphonated purple dye-stuffs from basic rosanilin. (Prod- 
uct, not process, claimed.) Diethyl dimethyl disulfo diphenyl para-rosanilin. 


Diethyl amino BENzoIc acid is condensed with methyl pIPHENYLAMIN by means of POCI,.. 
Blue vioLEer acid dye. 
S. 534—“‘Acid Violet 7B.” 


410,7839—Sept. 10, 1880. Traugott SANDMEYER, Switzerland. (Geigy.) 
Process of making aurin derivatives. Aurin tricarbo acid, Na salt. 


SaticyLic acid, 3 mols, is heated in sulfuric acid with NaNO, and meruyt alcohol, formal- 
dehyde, dioxy diphenylmethane dicarbo, or other. Red vioter acid mordant dyes. 
S. 557—‘‘Chrome Violet.” 


412,613—Oct. 8, 1889. Re. 11,077—May 20, 1890. Albert Herrmann, Germany. (Ho6chst.) 
Coloring-matter. (Process also claimed.) 3-Oxy dimethyl diethyl diamino triphenylcarbinol, 
homologs and derivs. 


3-Nitro BENZALDEHYDE is condensed with tertiary aromatic amins, reduced, and amino base 
converted into corresponding oxy comp. by nitrous acid. Or 3-oxy BENZALDEHYDE may be con- 
densed with tertiary amins. From resulting leuco bases the dye is formed by oxidation with 
peroxides. Either dye or its leuco base is sulfonated. Green-BLuE acid dyes, fast to washing. 

S. 54s—‘‘Patent Blue V.” Note 412,613, 14 and 15, 422,018, 453,477, 463,808, and Re. 
11,078 and 11,116. 


412,614—Oct. 8, 1880. Albert Herrmann, Germany. (Hochst.) 
Preparing coloring-matter. Tetra ethyl diamino 3-amino disulfo triphenyl carbinol sulfo 
acids. 


3-Nitro BENZALDEHYDE is condensed with diethyl anrL1n or other, reduced to form 3-amino 
tetra ethyl diamino TRIPHENYLMETHANE, sulfonated so that soluble ammonium salt may be 
formed, then oxidized and sulfo deriv. formed (or operations reversed). List of compounds to 
be used is given. Blue GREEN acid dyes. ‘ 

S. 543—‘‘Patent Blue V.’? Schulz fails to note that is a triamino comp. See 412,613 and 
412,615. 


412,614—Oct. 8, 1889. Re. 11,078—May 20, 1890. Albert Herrmann, Germany. (Héchst.) 
Coloring-matter. (Process also claimed.) Sulfo acids of 3-amino tetra alkyl diamino tri- 

phenyl carbinol. : 

3-Amino tetra ethyl diamino TRIPHENYLMETHANE or its carbinol deriv. is converted to sol- 
uble sulfo acid by heating in fuming sulf. (10-20 per cent anhyd), at 60° to 100°. Blue crEEN 
acid dyes. 

S. 543—‘‘Patent Blue V.” Reissue differs from original pat. in claiming product as well as 
process. 


412,615—Oct. 8, 1880. Albert Herrmann, Germany. (Hdéchst.) 
Coloring-matter. Tetra ethyl diamino 3-methoxy disulfo triphenyl carbinol. 


3-Methoxy BENZALDEHYDE or other, is condensed with diethyl anizin, or other, to form 3- 
methoxy tetra ethyl diamino triphenylmethane, or other, then sulfonated and oxidized. Or 3-oxy 
compound can be sulfonated then condensed with alkyl halogens. Green siusE acid dyes. 

S. 543—‘‘Patent Blue V.” Addition to 412,613. 


“nee 


GROUP XVIII.—TRIPHENYLMETHANE 291 


421,049—Feb. 11, 1890. Edward D. Kenpatt, New York. (Read-Holliday.) 
Sulphonating rosanilin. Sulphonating rosanilin by means of bisulfites, niter cake, etc. 


RosaNniILiIn HCl is dried, powd. and mixed with excess of fused anhyd. pulverized alk. bi- 
sulfate, or niter cake, heated in enameled vessel until HCl ceases to evolve and desired shade 
is attained. Rep acid dye. 

S. 524—‘Fuchsin S.” 


422,018—Feb. 25, 1890. Re. 11,116—Oct. 14, 1890. Albert Herrmann, Germany. (Hochst.) 
Blue-green dye. Sulfo derivs. of as-oxy tetra alphyl diamino triphenyl carbinols. 


3-Nitro BENZALDEHYDE is condensed with 2 mols. of two different tertiary amins, reduced 
and converted to oxy deriv. by warming with nitrite, etc. and sulfonated. Long list of com- 
ponents is given. Green BLUE acid dyes. 

S. 545—‘‘Patent Blue A.” Addition to 412,613. 


423,341—Mar. 11, 1890. Alcide F. Porrriger, France. 


Green dye. (Process also claimed.) Tetramethyl dibenzyl triamino 2-tolyl diphenyl car- 
binol disulfo. 


Tetra methyl diamino BENZHYDROL is condensed with 4-TOLUIDIN, 3-xylidin or other amin 
substituted in para position, by heating to 30° with conc. HCl or H,SO,, benzylated by BENzyL 
chloride and finally sulfonated. Resulting dye, with one amino group in meta position is GREEN, 
while para amino isomer is VIOLET. 


S. 523—‘“‘Fast Green extra.’’ Dye is credited by Schulz to Hassenhamp, same process. 
437,989—Oct. 7, 1890. Albert Herrmann, Germany. (Hochst.) 
Greenish-blue dye. Sulfo acid of dimethyl 3-amino tetramethyl diamino triphenyl car- 

binol. 


Dimethyl 3-amino tetramethyl diamino TRIPHENYL carbinol is sulfonated then oxidized. 
Or the sulfo acid of unsubstituted 3-amino compound is alkylated. Other components claimed. 
Green BLUE acid dye. 


453,47 7—June 2, 1891. Albert Herrmann, Germany. (Hodchst.) 
Blue-green dye. (Process also claimed.) 3-Chlor tetra ethyl diamino triphenyl carbinol 
sulfo. 


3-Amino tetra ethyl diamino TRIPHENYLMETHANE in 15 per cent HCl is diazotized and con- 
verted to meta Cl comp. (a) by heating with Cu,Cl in conc. HCl whereby N is liberated or (b) 
by mixing cold with 4 parts copper. Products are sulfonated at 60-70° with 5 parts fuming 
sulfuric (20 per cent SO,) till aq. sol. then oxidized in acid soln. by PbO,. Blue crexEn: acid 
dye. 

Addition to 412,613 and 14. 


463,898—Nov. 24, 1891. Albert Herrmann, Germany. (Hochst.) 
Blue dye. (Process also claimed.) Schulz states that methyl groups are probably eliminated 

by oxidation. 

3-Oxy tetramethyl diamino TRIPHENYL carbinol disulfo (Patent Blue V) or other meta oxy or 
meta amino carbinol is oxidized by Fe or Cr oxides. Buvue acid dye. 

S. 544—‘“‘Cyanin B.” Addition to 412,613. 


464,538—Dec. 8, 1801. Arthur Werinperc, Germany. (Cassella.) 
Violet dye. (Process also claimed.) Tetra methyl dibenzyl triamino triphenyl carbinol di- 
sulfo. 


Methyl benzyl anitin sulfo acid, or other, is heated with conc. soln. of FORMALDEHYDE then 
oxidized with dimethyl ANILIN at 40-50°. Or ethyl benzyl anilin sulfo, formaldehyde and di- 
methyl anilin are combined in strong sulfuric acid soln. VuioneT acid dyes. 

S. 530—‘‘Acid Violet 6B.” 


471,638—Mar. 29, 1892. Benno Homo.iKka, Germany. (Hoéchst.) 
Process of making rosanilin dyes. Triamino tritolyl carbinol. 


(a) Anhydro formaldehyde 2-toLuipin is heated to 170° with 2-TOLUIDIN, ANILIN, NITRO- 
BENZENE, and iron filings, (b) diamino DIPHENYL methane, 2-toluidin and 2-nitro toluol, or other, - 
are heated together with FeCl, or (c)diphenyl diamino diphenyl methane and diphenylamin, its 


292 DIGEST OF PATENTS 


HCI salt, 2-nitrotoluene, or homologs and FeCl, in HCl soln. ReEp to vIOLET to BLUE basic mor- 
dant and direct dyes. 

S. 513—“New Fuchsin O.” This is a process patent of general application with no dye 
claim but is classed as dye by Schulz. 


472,091—Apr. 5, 1802. Arthur WerIngerc, Germany. (Cassella.) 
Manufacture of blue dye. (Product also claimed.) Diethyl diamino ditolyl oxy disulfo 
phenyl carbinol. 

Ethyl 2-roLuipIn, 2 mols., condensed at 1oo° in dil. HCl soln. with 1 mol. 3-oxy BENZAL- 
DEHYDE to form sym-diethyl diamino ditolyl oxy PHENYL methane which is heated at 100° in 
conc. sulf. acid till sol. in aq. then oxidized. Buus acid dyes. 

S. 546—“‘Cyanol extra.” 


473,453—Apr. 26, 1892. Max Eptinc, Germany. (Héchst.) 
Red Dye. ‘Triamino triortho tritolyl carbinol trisulfo. 
Diamino diortho piToLyL methane is condensed with 2-to_uipin then sulfonated at 100—-120° 


in fuming sulf. (20 per cent anyhyd.). Rep acid dyes. 
S. 513—‘‘New Fuchsin O” sulf. 


476,413—June 7, 1802. Friedrich Runxet, Germany. (Bayer.) 
Triphenylmethane dye. (Process also claimed.) Tetramethyl diamino diphenyl oxy- 

carbo-naphthyl carbinol. 

Tetra methyl diamino BENZHyDROL is condensed in 66° H,SO, with 1-oxy NAPHTHOIC acid. 
BLvE basic mordant dyes. 

S. 567—“‘Chrome Blue Paste.’”? Note 476,414 which employs salicylic instead of naphthoic 
acid. 


476,414—June 7, 1802. Friedrich RuNKEL, Germany. (Bayer.) 
Triphenylmethane dye. (Process also claimed:) Tetra methyl diamino oxy carbo tri- 
phenyl carbinol. 
Tetramethyl diamino BENZHYDROL is condensed with 1 mol. saLicytic acid in 66° sulf. not 
above 40°, separated and oxidized. Red vioLer acid mordant dyes, suitable for printing and 


fast to soap. 
S. 549—‘‘Chrome Violet Paste.”? Addition to 476,413. 


478,005—June 28, 1892. Robert GnEHM and Jakob Scumuin, Switzerland. (Basle.) 
Violet dye. (Process also claimed.) 

Tetramethyl diamino BENZOPHENONE or other, in 80 per cent sulf. acid at O° is mixed with 
PYROGALLOL and HCl gas passed through the mixture. Other condensing agents may be used. 
VIOLET to blue acid mordant dyes, fast to soap and milling. 

Near S. 549—‘‘Chrome Violet.”’ 


484,697—Oct. 18, 1802. Rene Boun, Germany. (Badische.) 
Blue dye. (Process also claimed.) Tetra methyl 4.4’-diamino 2.”7”-dioxy diphenyl naphthyl 
carbinol. 


Tetra methyl diamino BENZOPHENONE is heated at 100° with ROCK. then 1 mol. 2.7-dioxy 
NAPHTHALENE is added and melt is further heated at 100°, cooled, and added to 30 per cent 
acetic to ppt. dye. Green BLUE acid mordant (Cr) dye. 


490,408—Jan. 24, 1803. Albert Herrmann, Germany. (Hochst.) 
Indigo-blue dye. (Process also claimed.) Constitution not claimed. 

3-Oxy, or 3-amino tetra methyl diamino TRIPHENYL carbinol disulfo or other meta substi- 
tuted tetra alkyl diamino triphenyl carbinol, is oxidized by Fe or Cr salts. Buiug acid dyes, 
faster to soap, light and air than other acid colors and of uniform shade. 

These are general claims for 463,898. Note also 412,613. 


496,435—May 2, 1803. Oscar NastvocEL, Germany. (Bayer.) 
Blue dye. (Process also claimed.) Tetra methyl diamino diphenyl benzyl-amino-naphthyl 
carbinol. 
Tetramethyl diamino BENZHYDROL condensed with 1 mol. benzyl 1-NAPHTHYLAMIN by heating 
in alc. soln. with glac. acetic, POCI,, etc., leuco product converted into nitrosamin by nitrite 


eS ey ee ees 


GROUP XVIII.—TRIPHENYLMETHANE 293 


in acetic HCI soln. oxidized by PbO,, then sulfuric added to remove Pb, and 4-roLuip1Nn, or 
other amin, to remove nitroso group (H,S or SO, may also be used). Product may be sul- 
fonated (in benzyl group) to an acid wool dye. Buus basic mordant dyes. 

S. 559—‘“‘Victoria Blue B.” Note 517,475. 


498,471—May 30, 1893. Huco HassENcAMP, Germany. (Bayer.) 
Triphenylmethane dye. (Process also claimed.) Tetramethyl disulfo dibenzyl triamino 
triphenyl carbinol. 


Dibenzyl ANILIN is sulfonated to para disulfo comp. in 4 parts fuming sulfuric (25 per cent 
anhyd.) at low temp., 1 mol. of product condensed by heating at 100° in 5 per cent sulfuric 
with 1 mol. tetra methyl diamino BENZzHyYDROL and oxidized in acetic soln. with PbO,, etc. vioLEeT 
acid dye fast to fulling and alk. and resembles Methyl Violet 5B. ' 

S. 523—‘“‘Fast Green extra.’’ Patent is a para disulfo compound while S. 523 is the meta 
deriv. 


501,069—July 11, 1893. Hugo HassencAmMp, Germany. (Bayer.) 
Violet dye. (Process also claimed.) Tetra methyl ethyl sulfo-benzyl triamino triphenyl 
carbinol. 


Tetra methyl diamino BENZHYDROL is condensed with ethyl benzyl anin1n disulfo by means 
of ZnCl, and NaCl. Blue vioret acid dyes, fast to fulling, very fast to alkali and without 
change in artificial light. 

S. 528—‘‘Fast Acid Violet 10B.”’ Note 611,609. 


501,104—July 11, 1893. Friedrich Runxet, Germany. (Bayer.) 
Triphenylmethane dye. (Process also claimed.) Tetra methyl diamino carboxy triphenyl 
carbinol. 


Tetra methyl diamino BENZHYDROL is condensed with BENZoIc acid using ZnCl, and NaCl. 
GREEN acid mordant (Cr acetate) dye, fast to fulling and suitable for printing on chromium 
mordant. 

S. 509—‘“‘Chrome Green Powd.”’ See S. 549—‘‘Chrome Violet.” Note 476,413-14. 


501,434—July 11, 1893. Carl Miuier, Germany. (Badische.) 


Violet dye. (Process also claimed.) Tetra methyl ethyl triamino trisulfo 2-methoxy tri- 
phenyl! carbinol. 


Resorcin and To_uipiIn (2 or 4) or homologs, are condensed to 3-hydroxy phenyl 4-ToLyL 
amin or other, heated in autoclave with NaOH, mrruyt chloride and mrtuyL alcohol to form 
alkyl ether then condensed with tetra methyl diamino BENZOPHENONE or. homolog using toluene 
as solvent, and POCI, or PHOSGENE, then sulfonated. VioLET BLUE acid dyes, fast to washing. 

S. s48—“‘Acid Violet 6BN.” 


506,918—Oct. 17, 1803. ™. Kotuer, F. ReEIncRuBER and H. Hassencamp, Germany. (Bayer.) 


Blue coloring-matter. (Process also claimed.) Tetra methyl triamino disulfo naphthyl 
diphenyl carbinol, or other. 

Tetra methyl diamino BEszHyDROL (or ethyl comp.) condensed with 1-NAPHTHYLAMIN 
2-sulfo or 2.4.7 trisulfo. Buus acid dye suitable for printing, fast to acids, alks., and not 
changed in artificial light. 

S. 562—‘‘Fast Acid Blue B.” 


517,473—Apr. 3, 1894. O. NastvocrL and F. Rerncruser, Germany. (Bayer.) 
Blue dye. (Process also claimed.) Tetra methyl diamino diphenyl ethyl amino naphthyl car- 
binol. 

Tetra methyl diamino BENZHYDROL or other, is condensed with 1 mol. ethyl 1-NAPHTHYL- 
AMIN by heating in alc. soln. containing glac. acetic or POCI,, converted to nitrosamin by HNO,, 
oxidized by PbO, and nitroso group removed by current of SO,. Bue basic mordant dye. 

S. ss8—“Victoria Blue R.” Addition to 496,435. 


519,971—May 15, 1894. J. Scumip and J. Bacue.ut, Switzerland. (Basle.) 
Blue dye. (Process also claimed.) Trimethyl diamino oxy disulfo diphenyl tolyl carbinol. 


3-Oxy BENZALDEHYDE, dimethyl aNILIN and methyl 2-TOLUIDIN, or other, are condensed, then. 
sulfonated and oxidized. Buus acid dye. 
Near S. 543—‘‘Patent Blue V.” 


294 DIGEST OF PATENTS 


525,627—Sept. 4, 1894. J. Scumip and J. BacuELur, Switzerland. (Basle.) 
Blue basic dye. sym-Dimethyl diamino 2-ditolyl dichlor phenyl carbinol. 

Methyl 2-roLuripin, or other, 2 mols., is condensed in alc. soln. with dichlor BENZALDEHYDE 
by heating at 100° with sulfuric acid, ZnCl,, etc., and leuco comp. oxidized in usual way with 
PbO,. Other components and dehydrating agents are claimed. Green BLUE basic mordant dye. 

S. 501—“‘Glacier Blue.”’ 


538,027—Apr. 23, 1895. Traugott SANDMEYER, Switzerland. (Geigy.) 
Blue dye. (Process also claimed.) Anhydride of tetra methyl diamino diphenyl sulfo tolyl 
carbinol. 

Tetra methyl diamino BENZHYDROL is condensed with 1 mol. 2-ToLuipin 5-sulfo by boiling 
in dil. sulf. acid, pptd., dissolved in dil. sulf. acid, equal vol. alc., then soln. of NaNO, and 
small amount Cu,O added (Griess reaction—substituting NH, by H), finally oxidized. Buiug 
acid dye. 

Near S. s07—‘‘Xylene Blue VS.” 


538,215—Apr. 23, 18095. Traugott SANDMEYER, Switzerland. (Geigy.) 
Blue dye. (Process also claimed.) sym-Trisulfo triphenyl rosanilin. 


DIPHENYLAMIN sulfo, 2 mols., is condensed with 1 mol. FORMALDEHYDE by refluxing at 
100-105° in acid soln., then oxidized with a third mol. of diphenylamin sulfo by boiling in acid 
soln. with Fe,Cl,. Biug acid and acid mordant dye. 

S. 538—‘‘Methyl Blue” or 539—‘‘Water Blue.” 


541,572—June 25, 1895. Friedrich RunxeL, Germany. (Bayer.) 
Blue-green dye. (Process also claimed.) Tetra methyl 4.4’-diamino diphenyl 4”-nitro 
tolyl carbinol. 


Tetra methyl diamino BENZHypROL is condensed with 4-nitro TOLUENE in conc. sulf. acid, 
below 50° at first then heated to 95°, leuco base separated and oxidized and ZnCl, double salt 
formed. Blue-crEEN basic mordant dye, suitable for printing. 

S. 498—“*Turquoise Blue B.”’ 


564,801—July 28, 1896. Traugott SANDMEYER, Switzerland (Geigy.) 
Greenish-blue dye. (Process also claimed.) Tetra methyl diamino 2-sulfo triphenyl car- 
binol anhydride, or other. 


2-Sulfo BENZALDEHYDE is boiled in dil. sulf. acid with 2 mols. dimethyl aniLIn, or ethyl 
benzyl anilin, then oxidized. Other components claimed. Green-sLukr acid dye, fast to alks. 
S. 506—‘“‘Erioglaucin A.” 


567,567—Sep. 8, 1806. Albert Herrmann, Germany. 


Blue coloring-matter. (Process also claimed.) Dibenzyl diamino ditolyl 3-oxy phenyl 
carbinol sulfo acid, or other. 
Benzyl 2-totuip1in, homologs or derivs., is condensed with 3-oxy BENZALDEHYDE then sul- 
fonated and oxidized. Burues acid dye. 
Near S. 545—‘‘Pat. Blue A” or S. 546—‘‘Cyanol extra FF.” 


580,186—Apr. 6, 1897. ; Albert Herrmann, Germany. (Hochst.) 
Blue dye. (Process also claimed.) Tetra methyl benzyl triamino diphenyl sulfo tolyl carbinol. 


Tetra methyl diamino BENZHYDROL, or homolog, is condensed with benzyl 2-toLurpIn sulfo 
then oxidized. Buiur acid dye, fast to soap, water, air and light. 
Near S. 527—‘‘Acid Violet 4BN” or S. 528—‘‘Fast Acid Violet 10B.’”’ Note 580,187-88. 


580,187—Apr. 6, 1807. Albert HERRMANN, Germany. (Hoéchst.) 
Fast blue dye. (Process also claimed.) Penta methyl triamino diphenyl sulfo tolyl carbinol. 


Tetra methyl diamino BENZHyDROL or homolog is condensed with methyl 2-ToLuip1N sulfo, 
then oxidized. Btiur acid dye, fast to water, air, soap and light. 
Addition to 580,186. 


580,188—Apr. 6, 1897. Albert Herrmann, Germany. (Héchst.) 


Blue acid dye. (Process also claimed.) Tetra methyl benzyl triamino diphenyl disulfo tolyl 
carbinol. 


GROUP XVIII.—TRIPHENYLMETHANE 295 


Tetra methyl diamino BENzHYDROL, or homolog, is condensed with benzyl 2-roLuipin di- 
sulfo and oxidized. Buur acid dye, fast to soap, water, air and light. 
Addition to 580,186. 


589,766—Sept. 7, 1897. Jules ViLu4, France. 
Red dye. (Process also claimed.) Rosolic acid hydroxyl replaced by one, two or three 

hydrazin groups. 

PueENnyL hydrazin (3, 2 or 1 mol), or other aromatic hydrazin, is refluxed in alc. soln. with 
rosoLic acid. Rep direct or acid mordant (Al) dyes. 

Near S. 556—‘‘Red Corallin.” Note 609,598 for closely similar process, and identical 
product. 


591,309—Oct 5, 1807. Jules Viti, France. 


Red dye. (Process also claimed.) Fatty hydrazin groups substituted for one, two or three 
hydroxyls in rosolic acid. 
Rosoxtic acid is condensed with fatty hydrazin, or homolog, by heating in closed vessel at 
100° with dil. NaOH. Rep direct dye. 
S. 556—‘‘Red Corallin.”” Note 609,598 and 664,450. 


603,016—Apr. 26, 1808. Arnold STEINER, Switzerland. (Sandoz.) 
Triphenylmethane-blue dye. (Process also claimed.) Penta methyl phenyl triamino 
diphenyl naphthyl carbinol. 

Methyl phenyl 2-NAPHTHYLAMIN or homolog is condensed with tetra methyl diamino BENzO- 
PHENONE and TOLUENE by emeans of POCI, then sulfonated. VuioLET to BLUE acid dyes, fast 
to alks. 

S. 561—‘‘Acid Violet 5BNS” and 565—‘‘Acid Blue B.”’ 


603,300—May 3, 1808. Henri Vipat, France. 
Process of making carboxylated products of triphenylmethane.  Trioxy 
carbo triphenyl carbinol. 

SaLicyLic acid, 1 or 2 mols, 3-oxy benzoic, 2-oxynaphthoic acid or amino carboxylic acids, 
PHENOL, and oxaLic or formic acid are condensed with sulfuric acid, or formic acid and ZnCl,. 
YELLOW to RED acid mordant dyes. 

Near S. 557—‘‘Chrome Violet.’”’ Note 609,599 for di- and tri-carbo compounds by similar 
process. Patent is classed as dye though claiming only a process. 


605,119—June 7, 1808. Oscar NastvocEL, Germany. (Elberfeld.) 
Diphenylnaphthylmethane dye. (Process also claimed.) Tetra methyl diamino di- 
phenyl sulfo-naphthyl methane sulfon anhydride. 

I-NAPHTHYLAMIN 5-Sulfo is condensed with tetra methyl diamino BENZHYDROL by heating 
at 80° in dil. sulf., separated, purified, diazotized, and SO, then copper powder added to diazo 
soln. below o° to form sulfinic deriv., purified, dissolved in alkali, hypochlorite added, finally 
oxidized. Other components claimed. Green BLUE acid dye, even dyeing and fast to alks. 

S. 563—‘‘New Patent Blue B.” 


609,598—Aug. 23, 1808. Henri R. Vipau, France. 
Red dye and process of making same. Constitution not claimed. 

Puenyy hydrazin, or other, is condensed with trioxy PHENYL carbinol carbo acid, or other, 
(with carbo group in meta or ortho position to amino or oxy group). Rep direct and acid 


mordant dye. 
Near 556—‘‘Red Corallin.” Note 580,766, 609,599 and 664,450. 


609,599—Aug. 23, 1808. Henri Vipat, France. 
Process of obtaining triphenylmethane derivatives. 4-Trioxy 3-tricarbo tri- 
phenyl! carbinol. 

Saticyiic acid, 3-oxy benzoic, oxy 2-naphthoic or 2- and 3-amino benzoic, etc., is heated 
with oxatic acid and sulf. acid (or formic acid and ZnCl,) in enameled kettle on oil bath. 
VARI-COLORED acid mordant dyes. 

S. 557—“‘Chrome Violet.’? Note 603,300 for similar process and product, and 401,739 (Sand- 
meyer) 1889, for different method for same product. Patent is classed as dye, though claiming 


only the process. 


296 DIGEST OF PATENTS 


611,628—Oct. 4, 1808. Hugo Hassencamp, Germany. (Elberfeld.) 
Violet dye and process of making same. Penta methyl sulfo benzyl triamino sulfo 
triphenyl carbinol. 


Methyl benzyl aniztin is sulfonated to disulfo comp. and condensed with tetra methyl di- 
amino BENZHYpDROL. Blue vioLer acid dye, fast to alks. 
S. 528—“‘Fast Acid Violet, 10B.’’ Addition to 501,069. 


615,472—Dec. 6, 1808. Emmanuel Bourcart, France. (Comp. Paris.) 
Green dye and process of making same. Nitro deriv. of 3-oxy tetramethyl diamino 
triphenylmethane disulfo. 


3-Oxy tetra methyl diamino TRIPHENYLMETHANE disulfo is dissolved at 50° in conc. sulf., 
cooled to 0° and HNO, added while keeping below 5°, the nitro leuco sulfo acid pptd. by neu- 
tralizing with alk. and oxidized. GreEen acid dye. 


615,485—Dec. 6, 1808. Carl Horrmann, Germany. (Hochst.) 
Green dye and process of making same. Dimethyl dibenzyl diamino 3-methoxy tri- 
phenyl carbinol mono, di or tri-sulfo. 


Dimethyl dibenzyl diamino BENZHYDROL, or other, is condensed with 3-methoxy BENZENE 
sulfo acid or other, sulfonated and oxidized. Grerrn acid dyes, fast to alks. 
Near S. s508—‘‘Xylene Blue AS.”’ 


621,893—Mar. 21, 1899. Henri R. Vipat, France. 
Triphenylmethane dye and process of making same. Constitution not shown, 
probably similar to 591,309. 
PHENYL hydrazin, its para sulfo comp. or other, is condensed’ with tetra methyl diamino 
BENZHYDROL, or other, in sulf. acid soln. without subsequent oxidation. ViIoLET to BLUE acid dyes. 
Note 591,309 and 609,598 for another application of hydrazins, and also 664,450. 


623,346—Apr. 18, 1899. Hugo Wet, Switzerland. (Basle.) 
Green-wool-dye and process of making same. Diethyl dibenzyl diamino nitro sulfo 
triphenyl carbinol. 
4-Nitro BENZALDEHYDE 2-sulfo acid is condensed with 2 mols. ethyl benzyl ANniLIN, or other, 
and carefully sulfonated. GrrEN acid dyes, fast to alks. and milling. 


628,243—July 4, 18809. Albert Herrmann, Germany. (Hochst.) 
Green acid dye. (Process also claimed.) Tetra methyl diamino diphenyl naphthyl carbinol 
sulfo. 


Tetra methyl diamino BENZHYDROL is condensed with NAPHTHALENE or other, then sulfonated 
and oxidized. GrrEen acid dye, fast to washing and light. 
S. 564—‘‘Naphthalene Green V.” Note 630,224. 


630,224—Aug. 1, 1899. Albert Herrmann, Germany. (Hochst.) 
Green dye and process of making same. Another process for tetra methyl diamino 

diphenyl naphthyl carbinol sulfo. 

Tetra methyl diamino BENZHYDROL, or other, is condensed with NAPHTHALENE 1.3-disulfo 
or other, then oxidized. Grern acid dyes. 

S. 564—‘‘Naphthalene Green V.”’ Note difference in process between 628,243 and 630,224 
consists only in sulfonation before or after condensation to triphenylmethane ferm. 


639,976—Dec. 26, 1899. Albert Herrmann, Germany. (Hochst.) 
Green dye. Tetramethyl 4-4’-diamino diphenyl 2”-6”-disulfo naphthyl carbinol. 

Tetra methyl diamino BENZHYDROL, is mixed with NAPHTHALENE 2.6-disulfo and added to 
sulfuric monohydrate, then heated at roo°® till sol. in dil. NH,, finally oxidized. GrrEn acid 
dyes, fast to washing, light, and level dyeing. 

S. 564—“‘Naphthalene Green V.” Note 639,977. 


639,977—Dec. 26, 1899. Albert HERRMANN, Germany. (Hochst.) 
Green Dye. ‘Tetramethyl 4.4’-diamino diphenyl 2”.7”-disulfo naphthyl carbinol. 

Tetramethyl diamino BENZHYDROL is mixed with NAPHTHALENE 2.7-disulfo and added to sul- 
furic monohydrate then heated at 100° till sol. in NH, finally oxidized. GreEn acid dyes, fast 
to washing, light and level dyeing. 

S. 560.—“Naphthalene Green V.”’ Addition to 639,976. 


GROUP XVIII.—TRIPHENYLMETHANE 297 


647,260—Apr. 10, 1900. 
Arthur HausporFer and Friedrich Reincruser, Germany. (Elberfeld.) 


Blue diphenylnaphthylmethan dye. (Process also claimed.) Sulfonated basic blues 
of Victoria Blue series. 


Night Blue, from tetramethyl diamino BENZOPHENONE condensed with 4/-tolyl 1-NAPHTHYL- 
AMIN, by means of POCL,, dissolved in sulfuric monohydrate and fuming acid (70 per cent 
anhyd.) added while keeping below 0°. Buus acid dyes. 

Near S. 560—“Night Blue.” 


658,504—Sept. 25, 1900. Oscar NastvoceL, Germany. (Elberfeld.) 
Blue diphenylnaphthyimethane dye and process of making same. Tetra 
methyl 4-ethoxy phenyl triamino diphenyl naphthyl carbinol sulfo. 


Tetra methyl diamino BENZOPHENONE is condensed with 4-ethoxy phenyl 1-NAPHTHYLAMIN, 
then sulfonated. Buius acid dyes. 
Near S. 559—‘‘Victoria Blue B” and s560—‘“Night Blue’”’ sulf. 


647,834—Apr. 17, 1900. Wilhelm Herzpere and Oswald ScHARFENBERG, Germany. (Berlin.) 
Green-blue dye. Tetra ethyl diamino diphenyl 3-oxy tolyl carbinol sulfo. 


Tetraethyl diamino BENZHYDROL and 2-TOLUIDIN in conc. sulf. are let stand at 20° for 12 
hours, resulting diphenyl 3-amino 4-tolyl methane diazotized then warmed at 50-60° in acid 
soln. to produce the meta-oxy comp., sulfonated at 20° with fuming sulfuric (60 per cent SO,) 
and finally oxidized. Green BLUE acid dyes. 


Near S. 543—‘‘Patent Blue V.’’ Patent claims that conc. instead of dil. acid for conden- 
sation causes the amino group of toluidin rest to take meta, not para, position to carbinol. 


661,800—Nov. 13, 1900. Hermann GutzkKow and Benno Homo.ika, Germany. (Hochst.) 
Process of transforming carbon dyes. 


BENZAL VIOLET, or other dye containing primary or secondary amino or hydroxyl groups, 
is condensed with an aromatic base containing two benzene nuclei united by -CH,.NH- or 
-CH,.NR-, such as 2-amino 3-xylyl 4-toluidin, by gently warming in aq. soln. or allowing to 
stand at usual temps. Products not described. 


664,450—Dec. 25, 1900. Henri R. Vipau, France. 
Triphenylmethane dye and process of making same. Constitution not shown. 
Probably similar to 591,309, 609,598, etc. 
Tetra methyl diamino BENZHYDROL, or other, is combined with 2-roty_ hydrazin, or other. 
VARI-COLORED basic mordant dyes. 


Addition to 621,393. 


668,580—Feb. 19, 1901. Tvan LEvInstE1IN and Richard Herz, England. (Levinstein.) 
Bluish triphenyl methane dye and process of making same. (Product not 
claimed.) Diethyl dibenzyl diamino nitro sulfo triphenyl carbinol. 


4-nitro TOLUENE 2-sulfo or other, is oxidized in alkaline NaOCl to form dinitro sTILBENE 2- 
disulfo acid, then oxidized by KMnO, to form 4-nitro 2-sulfo BENZALDEHYDE and condensed with 
ethyl benzyl anizin, or other. Green sBiuE acid dyes, fast to alkalies. 


673,632—May 7, 1901. Fritz Benper and Bertram Mayer, Germany. (Leonhardt.) 
Green-blue dye and process of making same. Tetra methyl diamino diphenyl tolyl 


carbinol disulfo. 
Tetra methyl diamino BENZHYDROL, or other, is condensed with toLuENE 4-sulfo acid or 
other, sulfonated to disulfo product and oxidized. Green BLUE acid dyes. 


Near S. 507—‘‘Xylene Blue VS.” 


676,555—June 18, 1901. Arthur Hausporrer, New York. (Elberfeld.) 
Blue triphenylmethane dye and process of making same. ‘Tetra methyl disulfo 
benzyl triamino diphenyl xylyl carbinol. 
Tetra methyl diamino BENZHYDROL, or other, is condensed with sym-3-XYLIDIN and BENZYL 
chlorid, then disulfonated. Buur acid dyes, fast to alkalies. 


298 DIGEST OF PATENTS 


677,279—June 25, 1001. F, RuNKEL, Germany. (Elberfeld.) 
Basic dye and process of making same. 


AuRAMIN G, (substituted auramins and ketones or thio ketones of similar structure) is 
heated in strong HCl soln. with 2-methyl 1npoL¥. A vioLET basic mordant dye, fast to acids. 


680,732—Aug. 20, 10901. Heinrich PowikiErR, Germany. (Berlin.) 
Blue acid dye. Sulfonated tetramethyl diamino diphenyl 1-dinaphthy] carbinol. 
Tetramethyl diamino BENZOPHENONE is condensed with 1-DINAPHTHYLAMIN and sulfonated 
in 1.5 parts fuming sulf. acid (about 20 per cent anhyd.) below 20° till soluble in alk. carb. soln. 
BLvueE acid dyes. 
Note 647,260, 688,966 and 496,435. 


684,367—May 25, 1807. J. Scumip and H. Wei, Switzerland. (Basle.) 
Blue-green dye. (Process also claimed.) Dimethyl dibenzyl diamino triphenyl carbinol 
disulfo. 


2-Chlor BENZALDEHYDE is sulfonated to meta sulfo acid then bisulfite added to form sBENz- 
ALDEHYDE 2.4- or 2.5-disulfo or dichlor BENZALDEHYDE is treated with bisulfite to form the (2.4) 
disulfo acid then product condensed with methyl benzyl aniLin, or other. Blue-crEEN to green 
BLUE acid dyes. 

Near S$. 508—‘‘Xylene Blue AS.”’ The similar dye S. 508 is credited by Schulz to Sterner, 
1902, pat. 731,139, which was issued five years later than above. 


684,45 7—Oct. 15, 1901. Heinrich Ponix1er, Germany. (Berlin.) 
Violet acid dye. Pentamethyl phenyl triamino diphenyl naphthyl carbinol. 


Tetra methyl diamino BENZOPHENONE is condensed with methyl phenyl 1-NAPHTHYLAMIN, 
then sulfonated. Vuzroxtet acid dyes. 
Near S. 559—‘‘Victoria Blue B’’ sulf. 


688,966—Dec. 17, 1901. Heinrich PoiikigerR, Germany. (Berlin.) 
Blue acid dye. Sulfo acid of tetramethyl diamino diphenyl methyl tolyl amino naphthyl car- 
binol. 


Tetramethyl diamino BENZOPHENONE is condensed with methyl 3-tolyl 2-NAPHTHYLAMIN and 
product warmed at 25-30° in 5 parts fuming sulf. (24 per cent anhyd.) Brus acid dyes, fast 
to washing. 

Addition to 680,732. 


688,967—Dec. 17, 1901. Heinrich Porikrer, Germany. (Berlin.) 
Blue dye. Penta methyl 3-tolyl triamino diphenyl naphthyl] carbinol. 


3-TOLUIDIN HCl and 1- or 2-NAPHTHYLAMIN (or naphthol) is heated to form 3-tolyl naph- 
thylamin, then alkylated to methyl 3-tolyl naphthylamin, finally condensed with tetra methyl di- 
amino BENZOPHENONE and TOLUENE using POCI,. Bux basic or direct dyes, fast to alkalies. 


701,427—June:3, 1902. Jules Vitix, France. 
Red dye and process of making same. Dioxy hexa alkyl triamino triphenyl carbinol. 


Diethyl 3-amino PHENOL or other, heated with cHLORAL in presence of oxidizing agent in 
glac. acetic acid soln. Rep basic dye. 


707,813—Aug. 26, 1902. Fritz Acu, Germany.. (Boehringer.) 
Triphenyl-methane dye and process of making same. Dimethyl diethyl dibenzyl 

triamino triphenyl carbinol, or other. 

Amino phenyl TartrRonic acid, acid K salt, is heated to 110-130° with ANILIN and NITRO- 
BENZENE in HCI sol. containing FeCl, Other components claimed. Violet direct dye. 

Near S. 529—‘‘Acid Violet 6 B.” 


709,160—Sept. 16, 1902. Joseph KortscHeEt, France. (Soc. Chim.) 
Green dye and process of making same. ‘Tetra methyl diamino diphenyl tolyl car- 
binol or sulfo acids. 
3-roLUYL aldehyde sulfo condensed with dimethyl aniLiIN or other. Blue GREEN to green 


BLUE acid dyes, fast to alkalies. 
Near S. 607—‘‘Xylene Blue S. conc.” 


GROUP XVIII.—TRIPHENYLMETHANE 299 


816,457—Mar. 27, 1906. Victor FusscAENGER, Germany. (Héchst.) 


Blue fibrous material and process of dyeing same. Tetra ethyl phenyl triamino 
triphenylmethane, or related comps. 


Fiber is saturated with mixture of alkyl diamino BENZHYDROLS and DIPHENYLAMIN derivs. 
and oxidized by means of chlorates and a catalyst such as cero chloride. Formulas are given. 
Fast BLUE basic mordant dyes, fast to aq., soap, dil. alks. and acids and reduced by hydrosulfites. 


835,682—Nov. 13, 1906. Wilhelm Hrrzperc and Oswald ScHARFENBERG, Germany. (Berlin.) 


Triphenylmethane dye and process of making same. Tetra ethyl diamino di- 
sulfo phenoxy triphenyl carbinol. 


Tetra ethyl diamino BENZHYDROL is condensed with 1 mol. as-2-amino 4-sulfo pIPHENYL, 
ether by heating to 95—100° in dil. sulf. acid, cooled, cryst., separated, and disulfonated in conc. 
sulf. acid. The amino group is removed by diazotizing in cone. soln. and adding alcohol and 
CuO, and product oxidized. Other components and reagents claimed. Green BLUE acid dyes, 
fast to alk. 


866,359—Sept. 17, 1907. William HrErzperc and Oswald ScHARFENBERG, Germany. (Berlin.) 
Triphenylmethan dye and process of making same. Diethyl disulfo dibenzyl di- 
amino 4-toluene sulfo ether of diphenyl tolyl carbinol. 
Saticyt aldehyde and roLvENE 4-sulfo chloride are combined to form 4-toluene sulfo ether 


of salicylic aldehyde, then condensed with benzyl ethyl ANILIN sulfo, or homologs. GREEN acid 
dyes, that are fast to washing. 


877,052—Jan. 21, 1908. Alfred Conzerti, Switzerland. (Geigy.) 
Triphenylmethane dye and process of making same. Dihydroxy dicarboxy di- 

tolyl 2-sulfo phenyl carbinol. 

2-Sulfo BENZALDEHYDE, the sulfo chlor, sulfo nitro or 2.4- or 2.5-disulfo or 2.4.5-disulfo 
methyl deriv., is condensed with 2-crEsotinic acid, salicylic acid or other aromatic oxy carbo 
acids, using nitrosyl sulfuric acid, or other oxidizing agents. Rep or violet BLUE acid and de- 
veloped (CrO,), or acid mordant dyes. 

S. 553—‘“‘Eriochromocyanin R.” Note 877,053-54. 


877,053—Jan. 21, 1908. Alfred Conzerti, Switzerland. (Geigy.) 
Triphenylmethane dye and process of making same. Dioxy dicarbo ditolyl 2-chlor- 

phenyl carbinol. 

2-Chlor BENZALDEHYDE, the dichlor, chlornitro, chlor sulfo, 2.4- or 2.5-disulfo or 2.4.5-tri- 
chlor deriv., is condensed with saticyLic acid, cresotinic acid, or other aromatic 2-oxy carbo 
acids. VIoLET or green BLUE developed (CrO,) or acid mordant (Cr) dyes suitable for print- 
ing and fast to milling and light. 

S. 551—‘‘Eriochromazurol B.”’ Note 877,052 and 887,620 for duplication of above process. 


877,054—Jan. 21, 1908. Alfred Conzerti1, Switzerland. (Geigy.) 
Triphenylmethane dye and process of making same. Dihydroxy dicarboxy di- 
tolyl dichlor phenyl carbinol, or other. 
2.6-Dichlor BENZALDEHYDE, trichlor, dichlér nitro or 2.6.5.-dichlor sulfo deriv., is condensed 
with 2-crEsoTINIC, salicylic or other 2-oxy carbo acid, and leuco dye oxidized with nitrosylsul- 
furic acid, etc. Rep and sur acid, acid mordant (Cr) or developed (CrO,) dyes suitable for 


printing. 
S. 554—“Chrom Azurol S.” Note 877,052 and 887,620 for similar process and product. 


886,815—May 5, 1908. Paul Junius, Germany. (Badische.) 

Green dye and process of making same. Tetra methyl diamino 2-sulfo triphenyl] 
methane with sulfo dinitro 4-anilino substituent in meta position to sulfo group. 
Meraniiic acid or deriv. is condensed with 2.6-dinitro chlor BENZENE 4-sulfo or (2.4.1.6) 

or deriv. to form 2.6-dinitro DIPHENYLAMIN 4.3/-disulfo or derivs., then combined with tetra 


methyl BENZHYDROL. GREEN acid dye. 
S. 542—‘“‘Agalma Green B.” 


887,620—May 12, 1908. Fritz FuNcCKE, Switzerland. (Basle.) 
Red triphenylmethane dye and process of making. Dihydroxy dicarbo ditolyl 2- 


chlor phenyl carbinol. 
20 


300 DIGEST OF PATENTS 


2-Chlor BENZALDEHYDE is condensed with 2 mols. 2-crEsotinic acid to 2-chlor phenyl dioxy 
ditolyl methane dicarbo acid and oxidized with HNO,. Rep, GREEN and BLUE acid and devel- 
oped (CrOQ,) dyes, which when chromed are fast to washing and Cl, and are adapted for print- 
ing on Cr mordant. 

S. 551—‘‘Eriochromazurol B.”’ Patent apparently duplicates 877,053. 


891,888—June 30, 1908. Max WEILER, Germany. (Bayer.) 
Diphenylnaphthylmethane dye. Tetramethyl diamino diphenyl 1-oxy 3.8-disulfo nap- 
thyl carbinol. 


Tetra methyl diamino BENZHyYDROL, or other, is condensed with 1-NAPHTHOL 3.8-disulfo. 
BLuE to GREEN acid dyes, fast to alkalies. 

Near S. 566—‘‘Wool Green S.”’ Schulz 566 employs 2-naphthol and sulfonates after con- 
densing with first component. Note 891,889. 


891,889—June 30, 1908. Max WEILER, Germany. (Bayer.) 
Diphenylnaphthylmethane dye. A trisulfo compound similar to previous patent. 


Tetra methyl diamino BENZHyYDROL, or other, is condensed with 1-NAPHTHOL 3.6.8-trisulfo. 
BLUE to GREEN acid dyes, fast to alkalies. 
Near S. 566—‘‘Wool Green S.”’ Addition to 891,888. 


947,876—Feb. 1, 1910. Max Weiler, Germany. (Bayer.) 
Red to violet wool dye. Dioxy dicarbo ditolyl oxy disulfo naphthyl carbinol. 
2-Oxy I-NAFHTHALDEHYDE 3.7-disulfo or other, is condensed with 2-crEsoTiINnic acid, or 


other. Rep to red-vioLtetT acid and acid mordant (Cr) dyes. 
Near S. 553—‘‘Eriochromcyanin R.” Note 877,052 and 887,620. 


950,359—Feb. 22, 1910. Max WEILER, Germany. (Bayer.) 
Orange-red to violet dye. Dioxy dicarbo ditolyl oxy phenyl carbinol. 
4-Oxy BENZALDEHYDE or other, is condensed with 2 mols. 2-crEsoTinic acid or other. Orange 


RED to VIOLET acid and developed (CrO,) dyes. 
Near S. 551—‘‘Eriochromazurol B.’”’ Note 877,052 and 887,620. 


976,417—Nov. 22, 1910. Max WEILER, Germany. (Bayer.) 
Dye. Probably diethyl amino dioxy dicarbo triphenyl carbinol and mixtures. 

Dimethyl ForMAURIN dicarbo leuco product, obtained from methylene 2.2/-pIcRESOTINIC acid, 
condensed at 100° in glac. acetic soln. with 1 mol. diethyl ANILIN, is oxidized at 30-40° in 
strong sulf. acid by nitrosyl sulfur‘c. Other components claimed. ReEpD to VIOLET to BLUE acid, 
developed (CrO,) and acid mordant dyes. 

Note 998,139. 


$978,799—Dec. 13, 1910. Max WEILER, Germany. (Bayer.) 
Aurin dye. 

Methylene 2.2/-di-crEsoriIniIc acid, or other, is condensed with 4-cRESoL in presence of ox- 
idizing agents such as nitrosyl sulf. Rep to vioLEeT acid, and acid mordant (Cr) or developed 
(CrO,) dyes. 

Near S: 556—‘‘Aurin.”” Note 978,800-02. 


978,800—Dec. 13, 1910. Max Weer, Germany. (Bayer.) 
Aurin dyestuff. 


Methylene 2.2/-di-crEsotinic acid, or other, is condensed with 2.6-dichlor PHENOL or other, 
in sulfuric acid containing an oxidizing agent such as nitrosyl sulfuric. Rep acid, and acid mor- 
dant (Cr) or developed (CrO,) dyes. 

Near S. 551—“‘Eriochromazurol.” Addition to 978,799. 


878,801—Dec. 13, 1910. Max WEILER, Germany. (Bayer.) 
Aurin dye. 

Methylene 2.2/-di-crEsSOTINIC acid is condensed with 2-NAPHTHOL 3.6-disulfo in sulfuric soln. 
with nitrosyl sulfuric acid or other oxidizing agent. Dye not described. 

Addition to 978,799. 


GROUP XVIII.—TRIPHENYLMETHANE 301 


978,802—Dec. 13, 1910. Max WEILER, Germany. (Bayer.) 
Aurin dye. 


Methylene 2.2’-di-crEsoTINIc acid is condensed with 4-cRESOTINIC acid by means of nitrosyl 
sulfuric acid. Vu1o.er acid and developed (CrO,) dyes. 


Addition to 978,799. 


995,494—June 20, rog11. August Stock, Germany. (Hochst.) 
Blue triphenylmethane dyestuff. (Process also claimed.) Probably contains a mix- 
ture of toluidin substitution products. 


4-Chlor BENZALDEHYDE is condensed with 2-crEsoTinic acid then heated with 4-ToLUIDIN or 
other. GRrry, VIOLET and violet BLUE acid and developed (CrO,) dyes, which when chromed are 
fast to milling and alks. 


Homolog of S. 556—‘‘Red Corallin.” 


998,1539—July 18, 1911. Max WEILER, Germany. (Bayer.) 
Greenish-blue triphenylmethane dye. Penta chlor phenyl dioxy dicarbo ditolyl car- 
binol. 
Penta chlor BENZALDEHYDE 1s mixed with 2 mols. 2-cREsoTINIC acid in conc. sulf. containing 


glac. acetic, and leuco dye oxidized by nitrite in acid soln. Brown and green BLUE acid and 
acid mordant dyes. 


999,028—July 25, 1911. Arthur HausporFer and Carl HreipENREICH, Germany. (Bayer.) 
Triphenylmethane dye. 2’.4’-Dinitro phenyl 5-amino 2-chlor phenyl dioxy dicarbo ditolyl 
carbinol. 


2-Chlor 5-amino BENZALDEHYDE is condensed with 2 mols. 2-cRESOTINIC acid and leuco prod- 
uct refluxed in dil. alk. carb. soln. with 2.4-dinitro chlor BENZENE, separated as Na salt and ox- 
idized in conc. sulf. by heating to 50° with nitrite. Other components claimed. Vari-cOLORED 
acid and acid mordant dyes, that are fast to potting and light when chromed. 


Near S. 551 to 554. 


1,004,609—Oct. 3, 1911. Max WEILER, Germany. (Bayer.) 
Triphenylmethane dye. Dioxy dicarbo ditolyl dibrom 3-oxy phenyl carbinol. 


2.4-Dibrom 3-0xy BENZALDEHYDE (2.6 or 4.6 derivs.) is condensed with 2-crESoTINICc acid. 
Green BLUE acid mordant (Cr) dyes that are fast to alkali and milling. One bath method may 
be used. 


Note 877,052 and 1,004,610. 


1,004,6i10—Oct. 3, 1911. Max WEILER, Germany. (Bayer.) 
Blue triphenylmethane dyestuff. Dioxy dicarbo ditolyl dichlor 3-oxy phenyl carbinol. 


2.6-Dichlor 3-oxy BENZALDEHYDE (2.4 or 4.6 deriv.) is condensed with 2-cRESOTINIC acid. 
Buus acid mordant (Cr) dyes, that are fast to alkali and milling. 


Addition to 1,004,609. 


1,023,977—Apr. 23, 1912. Max WEILER, Germany. (Bayer.) 
Dye. Dioxy dicarbo ditolyl phenyl methyl pyrazolon carbinol. 

Methylene 2.2’-di-cresoTinic acid or other, is oxidized and condensed with phenyl methyl 
PYRAZOLON, or other, in sulfuric acid soln. containing nitrosyl sulfuric, or other oxidizing agent. 
RED, VIOLET to BROWN acid, developed (CrO,) or acid mordant (Cr) dyes, for which one bath 
method may be used. 


Addition to 950,251—see Azo Dyes. 


1,026,089—May 14, 1912. Arthur HavusporFer, Germany. (Bayer.) 
Dye of the triphenylmethane series. Dioxy dicarbo ditolyl dibenzyl amino chlor 
phenyl carbinol, or other. 
2-Chlor 5-amino BENZALDEHYDE, or other, is condensed with 2 mols. 2-cRESOTINIC acid and 
with 2 mols. BENzyL chlorid in alk. soln. then sulfonated or not. Rep and sive acid and de- 
veloped (CrO,) dyes, which when chromed are fast to milling, potting and light. 


302 DIGEST OF PATENTS 


1,034,173—July 30,. 1912. Max WEILER, Germany. (Bayer.) 
Red-violet triphenyimethane dye. Trioxy tricarbo ditolyl xylyl carbinol. 


Methylene 2.2’-di-cREsOTINIC acid, or other, is condensed with sym-xXYLENOL 2-carbo acid or 
other. Vuroizt acid mordant (Cr) dyes. 


1,042,493—Oct. 29, 1912. August Stock and Friedrich Hrim, Germany. (Hodchst.) 
Dyestuff of the triphenylmethane series and process of making same. Dioxy 
dicarbo diphenyl] chlor toluyl carbinol substituted in toluyl residue, para position, by aryl 
amin. 
4.6-Dichlor ToLtuyy, 3-aldehyde is condensed with 2 mols. 2-crEsoTiINic acid and product 
heated with five parts ANILIN and one part ANILIN HCl at 100°. GRAy, VIOLET to BLUE acid 
and acid mordant dyes, fast to alkalies. 
Near S. 551 to 554. Note 995,494 and also 999,028 which is a meta substitution product 
while above is para. : 


1,044,833—Noyv. 19, 1912. Max WEILER, Germany. (Bayer.) 
Triphenylmethane dye. Dioxy dicarbo ditolyl chlor nitro phenyl ether of oxy dichlor 
phenyl carbinol. 
4’-Chlor 2/-nitro 3-phenoxy 2.6-dichlor BENZALDEHYDE or other, condensed with 2 mols. 
2-CRESOTINIC acid, or other. BLus to vioLtetT acid mordant (Cr) dyes for lakes. 


1,065,405—June 24. 1913. Re. 13,869—Aug. 24, 1915. 
: August Stock and Friedrich Heim, Germany. (Hodchst.) 
Dyestuffs of the triphenylmethane series and process of making same. Same 
as 995,494 except one hydroxyl group of cresotinic residue is in ortho and one in para 
position to carbinol. 
4-Chlor BENZALDEHYDE is condensed with 1 mol. each of 3-cRESOTINIC acid and 4-CRESOTINIC 
acid, oxidized and heated to 120° with 5 parts ANILIN and 1 part AnILIN HCl. Gray vioLer, 
VIOLET to BLUE acid and acid mordant dyes, fast to washing and milling. 
Addition to 995,494 and 1,042,498. 


1,101,770—June 30, 1914. Max WEILER, New York. (Synthetic.) 
Yellowish-zgreen triphenylmethane dye. Diethyl disulfo dibenzyl 4.4’-diamino di- 
tolyl 2”-chlor phenyl carbinol, or other. 
Ethyl sulfo-benzyl 3-roLUIDIN 2 mols., or other, is condensed with 2-chlor BENZALDEHYDE, 
or other. Yellow GREEN acid dyes, that are fast to alkali and fulling. 


1,149,575—Aug. 10, 1915. Rudolf Gartner and Georg Koures, New York. (Synthetic.) 
Triarylmethane dyestuff. Tetra ethy] diamino ditolyl chlor phenyl carbinol or other. 


Diethyl 3-roLurpIN, 2 mols. or other, is condensed with 2-chlor BENZALDEHYDE or other. 
GREEN to BLUE basic mordant dyes that are fast to light. 


1,217,238—Feb. 27, 1917. August Stock and Otto Nicop—EmMus, Germany. (Hdéchst.) 
Dyes of triphenylmethane series and process of making same. Dimethyl eth- 
oxy phenyl diamino diphenyl N-ethyl 2-phenyl indole carbinol sulfo, or other. 
4-Chlor dimethyl 4’-amino BENZOPHENONE or other is condensed with N-ethyl 2-phenyl 1n- 
DOLE, or other, then with 4-ANISIDIN, or other, and sulfonated. Vur1oLEt to BLUE acid dyes that 
are fast to light. 


1,218,232—Mar. 6, 1917. Max WEILER, New York. (Synthetic.) 
Blue triphenylmethane dye. Diethyl disulfo benzyl diamino ditolyl, tolyl amino phenyl 
carbinol or other. . ; 
BENZALDEHYDE, or other, is condensed with 2 mols. ethyl benzyl 3-roL_uipIN, or other, tri- 
sulfonated, oxidized and then heated with 4-TOLUIDIN, or other. VuIOLET to BLUE acid dyes that 
are fast to light and alkali. 


1,219,166—Mar. 13, 1917. - Julius Scumiptin and Max Fiscuer, Germany. 
Manufacture of chlorinated products of xylene, aldehydobenzoic acids, 
and dyestuffs therefrom. Dioxy dicarbo ditolyl trichlor carbo xylyl carbinol or other. 


3-XYLENE (or tech. product) is trichlorinated in nucleus, then tetra or penta chlorinated in 
side chains, oxidized to chlor-pIALDEHYDE or aldehydocarboxy product, finally condensed with 


yee 


4 
j 
q 
, 
| 


= 


GROUP XVIII.—TRIPHENYLMETHANE 303 


2 mols. 2-cRESOTINIC acid or other. Blue vio.zt and brown rep acid and developed (CrO,) dyes, 
which when chromed are fast to washing and milling. 


1,244,149—Oct. 23, 1917. Max Weiter, New York. (Synthetic.) 
Violet cotton-dye. Triphenylmethane dye sulfonated in meta position of anilino group. 
4-Toluidino dimethyl dioxy dicarbo TRIPHENYLMETHANE (from BENZALDEHYDE condensed with 
2-CRESOTINIC acid, oxidized, sulfonated, and condensed with 4-ToLUIDIN), or other, mono sulfo- 
nated, in fuming sulf. acid. Vuio.trt acid mordant (Cr) dye. 
Near S. 551—‘“‘Eriochromeazurol.”’ 


1,387,596—Aug. 16, 1921. 
Guillaume Montmo.iin and Heinrich J. Spreter, Switzerland. (Basle.) 

Dyestuffs and process of making same. Aurins of naphthalene series (probably). 

I-NAPHTHOL, or deriv. with 4-position not substituted, 3 mols., in strong NaOH soln., is 
mixed with 1 mol. tetra chlor METHANE and a little Cu powd. at usual temp. or refluxed. Other 
alkali or alkali earth hydroxide, oxides and carbonates may be used and as catalyst a copper 
comp. as well as the metal. Blue vioLeT to BLUE acid and acid mordant or developed (CrO,) 
dyes, fast to fulling and potting. 


1,402,195—Jan. 3, 1922. Harlan L. TrumsButy and William L. Evans, Ohio. (U. S. Gov.) 
Process for making crystal violet. Improved process for Crystal Violet. 


Dry CHLOR PICRIN mixed with dry dimethyl anrL1n is heated to 100° and a small amount 
AICI, added as catalyst. Brown and violet fumes are evolved, VuioLet basic mordant dye. 


1,428,984—Sept. 12, 1922. Junius ScumiIpLIN, Germany. (Cassella.) 
Manufacture or production of chlorinated products of toluene and dye- 
stuffs therefrom. Tetra chlor phenyl dicresotinyl carbinol. 
Tetra chlor BENZALDEHYDE is condensed in conc. H,SO, with 2 mols. crEsorinic acid and 
oxidized by adding NaNO,. A RED to BROWN or green BLUE acid or acid mordant (Cr) dye 
which when after chromed is fast to washing, milling and potting. 


1,430,8998—Oct. 3, 1922. Fritz GuntHER, Germany. (Badische.) 
Manufacturing yellow coloring matters for dyeing animal fibers. (Product 

also claimed.) Di or triphenylmethane dyes. 

2-Nitranilin, or derivs. with para position to NH, unsubstituted, and from 0.33-1 parts 
BENZALDEHYDE or other, are condensed by heating at 85° in HCl soln. (2°), excess reagents 
removed by steam distillation and dried product sulfonated at 85° in H,S0, (66°). Or ‘sulfo 
deriv. of benzaldehyde may be used and later sulfonation omitted. The 2 resulting dyes may 
be separated by soln. of one in 25° HCl. Green-yELLow acid dyes, even dyeing and fast to 
light, milling, acids and alks. 


1,460,315—June 26, 1923. 
Guillaume de MontTMOLLIN, Josef SpreLER and Gerald Bonuore, Switzerland. (Basle.) 


Dyestuffs of the triarylmethane series and process of making same. 

I-NAPHTHOL or deriv., with free 4-position, in nearly 4 parts 15 per cent NaOH is mixed 
with o.s mol, puENyL chloroform, or other aryl chloroform, diluted and dye salted out. Copper 
or other catalyst may be used and other binding agents for acid that is generated. Dark powds., 
sol. NaOH (GB-G), in conc. sulf. (Br-B); the 2-carbo deriv. of naphthol is a GREEN acid mor- 
dant (Cr) dye. 


1,470,554—Oct. 9, 1923. Augustus Edward Craver, New York. (Barrett.) 
Dyestuff prepared from orthoxylylaldehyde. ‘Triphenylmethane dye from 3.4-di- 
methyl benzaldehyde sulfo acids. 

The mono or di sulfo acid of 3.4-dimethyl BENZALDEHYDE (obtained by catalytic oxidation 
of ps-cUMENE) is made by adding the aldehyde to 5 parts fuming sulf. (63 per cent SO,) at 
0-5° or to 8 parts at 80-150°, and 1 part of the free acid separated in usual way with Ca or 
BaCO, is condensed with 1.26 parts dimethyl-anizin by boiling in 10 parts aq. containing 0.12 
per cent H,SO,. The leuco base is oxidized in the usual manner with PbO,. Blue Green acid 
dyes, fast to alks., light and washing. 


304 DIGEST OF PATENTS 


1,470,555—Oct. 9, 1023. Augustus E. Craver, New York. (Barrett.) 
Dyestuff prepared from orthoxylylaldehyde. Triphenylmethane dye from 3.4- 
dimethyl benzaldehyde. 
Process is similar to 1,470,554 except that benzaldehyde is not previously sulfonated. One 
part 3.4-dimethyl BENZALDEHYDE and 1.96 parts dimethyl aNniILIN are refluxed with 1.74 parts 
conc. HCl (1.20) at 100° for 24 hours, unchanged reagents removed by steam distn. and sep- 


arated leuco base oxidized with PbO, in usual way. Other similar aromatic amins are claimed. 


Blue GREEN to BLUR basic and basic mordant dyes. 

1,478,015—Dec. 18, 1923. Don W. Bissett, New York. (National.) 

Production of triphenylmethane dye. 3-Oxy tetraethyl diamino triphenyl car- 
binol, disulfo acid, by improved method. 


3-Oxy tetraethyl diamino TRIPHENYLMETHANE disulfo acid is produced by condensing 
3-Oxy BENZALDEHYDE with diethyl ANILIN in presence of H,SO,, then sulfonating with oleum to 
disulfo deriv. Product is dissolved in acetic acid and oxidized with PbO, to form the carbinol. 
GREEN acid dye. 


1,478,039—Dec. 18, 1923. Lucas P. Kyripes, New York. (National.) 
Triarylmethane dyes. 


Two mols. N-oxy ethyl benzyl aANILIN are condensed with 1 mol BENZALDEHYDE 2.5-disulfo 
by refluxing 30 hours in 8 parts aq., leuco product purified and oxidized by PhO, in acetic acid 
soln. Other similar comps. claimed. GREEN to BLUE acid dyes suitable for lakes. 


Group XIX.—XANTHONE. 


377,349—Jan. 31, 1888. Maurice CERESOLE, Germany. (Badische.) 
Production of new red coloring-matter. (Product, not process, claimed.) Tetra 
methyl rhodamin. 


Dimethyl 3-amino PHENOL and PHTHALIC anhyd. heated in enameled digester at 175° out of 
contact with air, powd. melt digested at 20° with weak NH, (18 per cent) color base extracted 
with benzin and removed therefrom as soluble hydrochloride by hot dil. HCl. Rep direct and 
basic mordant dye, fast to air and light. : 

S. 573—‘Rhodamin B.” 


377,350—Jan. 31, 1888. Maurice CrrEsoLt, Germany. (Badische.) 
Production of new red coloring-matter. (Product, not process, claimed.) Tetra 
ethyl rhodamin. 


Diethyl 3-amino PHENOL heated in enameled digester at 175° with PHTHALIC anhyd., puri- 
fied and separated as HCI salt. Rep direct and basic mordant dyes, faster to air and light than 


eosins. 
S. 375—‘‘Rhodamin D.” 


402,436—Apr. 30, 1889. Robert GNEHM, Switzerland. (Basle.) 
Red carbon color. Succinein of tetra ethyl diamino xanthone. 


Diethyl 3-amino PHENOL is condensed at 195-205° with succinic acid by means of ZnCl. 


Rep basic dye. 
S. 570o—‘‘Rhodamin S.” 


413,048—Oct. 15, 1880. Robert GNEHM and Jakob Scumip, Switzerland. (Basle.) 
Violet coloring-matter. Diphenyl 2.7-diamino phenol phthalein. 

3-Oxy DIPHENYLAMIN, 2 mols., is mixed with 1 mol. PHTHALIC acid and ZnCl, and heated 
at 160-170°. Vi10LET basic dye. 


413,049—Oct. 15, 1880. Robert GneuHM and Jakob Scumip, Switzerland. (Basle.) 
Blue coloring-matter. Diphenyl dichlor rhodamin. 
3-Oxy DIPHENYLAMIN, 2 mols., is heated at 170-200° with 1 mol. dichlor pHTHaALic acid and 


ZnCl. 
Near S. s80—‘Fast Acid Violet.” Note 413,048 and 413,050, which is the tetra chlor deriv. 


Patent is wrong in calling this a phthalein. 


CE ee ey COE ee geen een ee eee 


GROUP XIX.—XANTHONE 305 


413,050—Oct. 15, 1880. Robert GNEHM and Jakob Scumip, Switzerland. (Basle.) 
Gray coloring-matter. Diphenyl 2.7-diamino tetra chlor phenolphthalein. 


Tetra chlor PHTHALIC acid is condensed with 2 mols 3-oxy DIPHENYLAMIN by heating at 
180-210° with ZnCl, Gray basic dye. 


425,504—Apr. 15, 1890. Robert GNEHM, Switzerland. (Basle.) 
Red dye. Succinein of tetra methyl diamino xanthone. 

Succinic acid anhyd. mixed with ZnCl, is heated to 190°, dimethyl 3-amino PHENOL added 
and temp. kept below 210° till reaction is finished. Rep basic and basic mordant dye. Process 
differs from 402,436 by adding the amino phenol to the hot melt of the acid and condensing 
agent. 

S. 570—‘‘Rhodamin S.” 


438,053—Oct. 7, 1890. Hermann BorpEKER, Germany. (Hochst.) 
Violet dye. Sulfo acid of 4'4”-ditolyl rhodamin. 

2’ or 4’-Ditoly] RHODAMIN is slowly added to 6-8 parts H,SO, mono hydrate. Red vioLEr 
(ortho deriv.) to blue vioter (para) basic dyes. 


445,684—Feb. 3, 1801. Fritz BenpErR, Germany. (Miuhlheim.) 
Pink dye. (Process also claimed.) Tetra alkyl diamino xanthone. 

Dimethyl 3-amino PHENOL is digested at usual temp. in alc. soln. with FORMALDEHYDE. Sol- 
vent may also be aq. NaOH or HC! at 50-60°. Product is further treated at 100° in conc. 
H,SO, to remove a second mol. of H,O and finally oxidized with FeCl, or other, to a xanthone. 
Rep basic dyes. 

S. 568—‘“‘Pyronin G.” 


449,520—Mar. 31, 1801. Maurice CERESOLE, France. (Badische.) 
Benzo-rhodamine. Tetra methyl decarboxylated rhodamin. 
Benzo trichloride heated to 100° in closed vessel with 2 mols. dimethyl 3-amino PHENOL 
in toluene as solvent, purified and pptd. with NaCl and ZnCl,. Rep basic mordant dye. 
“Benzo-Rhodamin.”’ 


456,081—July 14, 18091. Maurice CERESOLE, France. (Badische.) 
Red dyestuff. Diethyl rhodamin. 

Ethyl 3-amino PHENOL, 2 mols., is heated in closed vessel without air with PHTHALIC anhyd. 
and ZnCl, to 170-180°, diluted and digested with NH,. Rep direct dye. 

Schulz gives Bernthson credit for this dye, 1892. 


489,923—Jan. 10, 1893. Fritz BeEnpER and Michael KamMMERER, Germany. (Milheim.) 
Yellow-red dye. (Process also claimed.) Dyes from rhodamins by oxidation. 


Ruopamin dye is dissolved in dil. acetic acid and KMnO, carefully added, at usual temp. 
Violet red dyes become orange red by treatment. Orange RED basic dyes. 


493,241—Mar. 14, 1893. Hermann BorpEKER, Germany. (Hochst.) 


Pink dye. 

Fiuorescein chloride is heated to 200-210° with mEsipIN and ZnCl,, and the purified dry 
product added to fuming sulf. acid (5 per cent anhyd.) at 20-25° to form sulfo acid. RED acid 
dye fast to light, fulling and soap. 

Prosper Monnet, France. (Soc. Chim.) 


499,927—June 20, 1803. 
Tetra methyl 3.3’-diamino phenolphthalein diethyl 


Anisolin and process of making it. 
ether, or ‘‘anisolin.” 

Tetra methyl 3.3/-diamino PHENOLPHTHALEIN, OF other, dissolved in boiling aq. 
into boiling dil. KOH and resulting K salt in alc. soln. with EruyL chloride or other alkyl or 
aryl halogen deriv., heated under pressure at 100-120°. Rep direct dyes. 

S. 574—‘“Rhodamin 3B.” 


is poured 


516,584—Mar. 13, 1894. Heinrich A. Berntusen, Germany. (Badische.) 


Red dye. Dialkyl rhodamin alkyl ester. 


Diethyl RHODAMIN made as in 456,081, or deriv. 
usual temp. then preferably refluxed on water bath. 


, in alc. soln. is saturated with HCl gas at 
Other acids may be used and different 


306 DIGEST OF PATENTS 


alkyl. radicals introduced by varying the alcohol or using alkyl halogens. Rep basic and basic 
mordant dyes. 
S. 571—‘“‘Rhodamin 6G.”’ 


516,585—Mar. 13, 1894. Heinrich A. Berntusen, Germany. (Badische.) 
Red rhodamin dye. (Process also claimed.) Dialkyl homo rhodamin alkyl ester, 

Ethyl amino crEsoL, 2 mols., heated at 170-200° with puTHaLic anhyd. and ZnCl,, latter 
removed by washing and product digested with NaOH, to form diethyl homo RHODAMIN base, 
which is dissolved in alcohol through which dry HCl gas is passed, preferably while refluxing 


on water bath. Other components and materials claimed. Rep basic mordant dye. 
Near S. 571—‘‘Rhodamin 6G.” Addition to 516,584. 


516,588—Mar. 13, 18094. Maurice Crrresoie, France. (Badische.) 


Rhodamin dye. (Process also claimed.) Tetra alkyl rhodamin dyes converted to yellower 
shade by splitting off one or more alkyl groups. 


Tetra ethyl RHopAmiIN of phthalic acid series, or other, is heated gradually to about 235° 
alone or in an indifferent solvent such as naphthalene, with anilin HCl, which takes up alkyl, 
or with ZnCl,. Rep basic dyes of yellower shade than original rhodamin. 

S. 572—‘‘Rhodamin G.”’ 


516,589—Mar. 13, 1894. Maurice CERESOLE, France. (Badische.) 
Rhodamin dye. as-Trimethyl rhodamin. 


Tetramethyl RHODAMIN of succinic acid series, together with equal weight of anizin HCl 
is heated gradually to 1oo° and kept at this temp. until test shows desired amount of de-alkyl- 
ation. Rhodamin may also be heated alone, in naphthalene or with ZnCl,. Rep basic and 


basic mordant dye. 
Near S. 570—‘‘Rhodamin S.” Note 516,588. 


551,885—Dec. 24, 18095. Joseph BIERER, Switzerland. (Durand) 
Blue dye and process of making same. 


Diethyl amino azo BENzIDIN HCl or nitroso diethyl anilin, is condensed with GaLLAmic acid 
to a gallocyanin then heated at 50° with AaniLin, or other, higher temps. producing greener 
shades. Product may be sulfonated. Buiug acid and acid mordant dyes. : 

Near S. 641—‘‘Corein R. R., powd.’’ 


573,299—Dec. 15, 1806. Traugott SANDMEYER, Switzerland. (Geigy.) 
Red dye. (Process also claimed.) Rhodamin dyes with sulfo for carbo group. 


BENZALDEHYDE 2-sulfo, 10 per cent soln. is boiled with 2 mols diethyl 3-amino PHENOL, 
evap. to dryness, heated at 135-140° in conc. H,SO,, and oxidized with FeCl,. Sulfuric acid 
treatment may be made to include preceding operation. Rep acid dyes. 


576,222—Feb. 2, 1897. Carl Oscar MvuELLER, Switzerland. (Basle.) 
Rhodamin dye. (Process also claimed.) Unsymmetrical rhodamin dyes. 


Dimethyl amino oxy benzoyl sBenzorc acid, derived from PHTHALIC anhyd. and 1 mol. di- 
ethyl 3-amino PHENOL, is condensed with another mol. diethyl 3-amino phenol by_ heating at 110° 
in 98 per cent H,SO,. Other components claimed. Rep basic and basic mordant dyes. 


Note 578,578. 


576,223—Feb. 2, 1897. Carl Oscar MuELLER, Switzerland. (Basle.) 
Rhodamin dye. (Process also claimed.) Rhodamin dyes changed to ether form. 


Dimethyl amino oxy benzoyl BENzorc acid, derived as in 578,578 from PHTHALIC anhyd. and 
1 mol. diethyl 3-amino PHENOL, is heated at 110° in 98 per cent HS0, with a second mol. of 
same phenol and separated product heated in alcohol containing HCl. Violet rEp basic dyes. 


578,578—Mar. 9, 1897. Carl O. MuE.ier, Switzerland. (Basle.) 
Rhodamin dye. (Process also claimed.) Unsymmetrical trimethyl rhodamin. : 


Dimethyl 3-amino PHENOL and equal parts pHTHALIC anhyd. are heated together at 100° 
and resulting dimethyl amino oxy benzoyl BENzoIc acid condensed with 1 mol. 3-amino 4-CRESOL 
by heating in 98 per cent H,SO, at 140-160°. Rep basic mordant dye. 


GROUP XIX.—XANTHONE 307 


584,119—June 8, 1897. j Carl O. Mur.ier, Switzerland. (Basle.) 
Rhodamin dye. Alkylester and inner anhydride of rhodamin. 

@S-RHODAMIN’ derived as in 578,578 is heated in alc.-sulf. acid soln. for 8 hours. Rep basic 
mordant dye. 

S. 576—“Rhodamin 3G,” or 577, ‘“‘Rhodin 2G.” 


596,333—Dec. 26, 1897. Carl Oscar Mueuuer, Switzerland. (Basle.) 
Rhodol dye. (Process also claimed.) ‘“Rhodols’” or rhodamin in which one NH, is re- 
placed by OH. 
Dimethyl amino oxy benzoyl BENnzorc acid is heated at 100° with 1 mol. RESORCINOL in conc. 


H,SO, mixed with equal volume aq., soln. diluted and further heated. Orange rep basic mordant 
dyes. 


609,99 7—Aug. 30, 1808. Jakob ScuHmip and Hermann Rey, Switzerland. (Badische.) 
Red-violet phthalein dye. (Process also claimed.) Tolyl rhodol. 

Condensation product from 1 mol. each of PHTHALIC anhyd. or halogen derivs. and 3/-oxy 
phenyl 2-ToLyL amin, mixed with 1 mol. REsoRcINoL and KHSO, is heated to 170-175° tor 1 
hour. Violet RED to red vioLtET acid dye, fast to air and light and level dyeing. 

Note 413,048. 


609,998—Aug. 30, 1808. Jakob Scumip and Hermann Rey, Switzerland. (Badische.) 
Sulfonated monobenzyl-phthalein dye. (Process also claimed.) as-Benzyl trialkyl 
diamino phenolphthalein. 
Ethyl benzyl 3-amino PHENOL is fused with 1 mol. PHTHALIC anhyd. at 130—-140° and prod- 
uct together with 1 mol. diethyl 3-amino pHENoL and KHSO, is heated to 175°, product sep- 
arated and sulfonated in fuming HWSO, (30 per cent SO,) below 15°. Rep basic mordant dye. 


613,113—Oct. 25, 1898. Johann J. Brack, Switzerland. (Basle.) 
Rhodol derivative and process of making same. (Process also claimed.) Tetra 
methyl dirhodol methane (probably.) 

Dimethyl ruopo. ethyl ether, 1 mol., mixed in 66° H,SO, with 2 mols. FORMALDEHYDE and 
let stand several days. Resulting dye sulfate is converted to chloride by treating its alcohol 
soln. with HCl. Orange rep basic mordant dye, suitable for printing with ferrocyanide and 
ZnO. 

S. 578—“Rhodamin 12 GF.” Note 625,536 and 643,371. 


613,926—Nov. 8, 1808. Carl Horrmann, Germany. (Hoéchst.) 
Red rhodamin dye and process of making same. Rhodamin dialkyl amins. 


Diethyl rHopAMin HCl, 1 part, is mixed with 3 parts POCI,, heated to 80°, cooled and ex- 
cess POC], removed by benzene. Dikruyt amin or homolog is next carefully added in a sol- 
vent such as CHCIl., keeping temp. low, and then mixture warmed at 50°. Rep basic dyes. 


615,791—Dec. 13, 1808. © Hermann BorepEkErR, Germany. (Hochst.) 
Process of making sulfonic acids of asymmetric rhodamins. (Product also 
claimed.) as-Rhodamin sulfo acid. 


Friuorescein chloride is mixed in phenol soln. with 1 mol. 2-toLuiptn HCl and heated at 
180°. Other primary or secondary bases may be used. The condensation product and another 
mol. 2-ToLUIDIN and mono or DIETHYL amin are heated with ZnCl, and CaO to 190-200° to 
form a rhodamin that is sulfonated in eight parts conc. H,SO, at 40-45°. Rep acid dye. 


617,627—Jan. 10, 1899. Oscar Batty, Germany. (Badische.) 
Process of making green dyes. Hydrolyzing brom fluorescein with the aid of boric acid. 


Equal parts of dibrom or tetrabrom FLUORESCEIN and boric acid are heated at 240-250° in 
to parts 66° H,SO, until brom product has disappeared. Green acid mordant dyes. 


624,877—May 9, 1899. Jakob Scumip and Hermann Rey, Switzerland. (Badische.) 
Red sulfo-acid dye. (Process also claimed.) Making rhodamin dyes by dehydrating, 
sulfonating and oxidizing in one operation. 
One mol. BENZALDEHYDE or deriv. and 2 mols. ethyl benzyl 3-amino PHENOL are refluxed in - 
equal parts alcohol and 10 per cent H,SO, soln. and resulting leuco body heated at 130° in 3 


308 DIGEST OF PATENTS 


parts conc. H,SO,, separated and oxidized in 10 per cent FeCl,. Rep acid dyes, fast to light, 
acids and alks. 


625,536—May 23, 18909. Johann J. Bracx, Switzerland. (Basle.) 
Rhodol derivative. 


Dimethyl rHopoL, methyl ether, in 6 parts 66° sulf. acid, is mixed with 1 mol. FORMALDE- 
HYDE, let stand at room temp., diluted with ice and pptd. by salt. REp basic mordant dye suit- 
able for lakes with K,Fe(CN), and ZnO. 

For ethyl ether of above dye, see 613,113. 


625,641—May 23, 1890. Heinrich Caro, Germany. (Badische.) 
Rhodamin dye and process of making same. 


CuioraL hydrate, 1 part, and 3 parts diethyl 3-amino PHENOL, or other, ground together, 
mass powd. and dried in thin layers at 40-70°, leuco product oxidized in HCl soln. by FeCl,, 
using salt or nitrate to ppt. dye and remove it from danger of excess oxidation, and separated 
product let stand in aq. soln. till red color develops. Other reagents and unsymmetrical prod- 
ucts also claimed. Rep, direct and basic mordant dye. 


633,883—Sept. 26, 1890. Carl O. MUELLER, Switzerland. (Badische.) 
Yellow basic dye. By-product from rhodamin mfr., valuable as dye. 


Dialkyl rhodamin produced in usual way from ethyl 3-amino PHENOL, 2 mols. and PHTHALIC 
anhyd. with ZnCl, as in 456,081, is filt.; to remove rhodamin, by-product in mother liquor is 
pptd. with HCl, heated at 150-160° with 30 per cent NaOH in autoclave, pptd. with HCl, prod- 
uct esterified in alc. sulf. acid mixture and finally pptd. as HCl salt. Yellow basic and basic 
mordant dye. 


641,184—Jan. 9, 1900. Hermann BorpEKER, Germany. (Hoéchst.) 
Rhodamin dye. 

Diethyl rRHopAMIN, or homolog, is mixed with equal parts methyl anit1n and POCI, slowly 
added, keeping temp. below 20-25°. Other aromatic secondary or tertiary amins, or quinolin, 
etc., may be used. Pale rep (pink) basic mordant dyes. 


642,893—Feb. 6, 1900. Hermann BorpEKER and Carl HorrMann, Germany. (Hochst.) 
Alkylated rhodamin sulfonic acid. 

Diethyl 3-amino PHENOLPHTHALEIN is slowly added to 6 parts fuming H,SO, (10 per cent 
SO,) below 20°. Rep acid dye. 

S. 581—‘‘Fast acid Eosin G.” 


643,371—Feb. 13, 1900. Johann J. Brack, Switzerland. (Basle.) 
Red rhodamin dye. Tetra methyl dirhodamin methane, diethyl di ester. 

Ethyl ether of as-trimethyl RHODAMIN derived from dimethyl amino oxy benzoyl BENzoIC 
acid and 3-amino 4-cRESOL, 2 mols, is condensed with 1 mol FORMALDEHYDE in conc. H,SO,, then 
pptd. as HCI salt. Rep basic mordant dye. 

Near S. 578—‘“‘Rhodamin 12GF.”’ Note 584,119 and 613,113. 


645,781—Mar. 20, 1900. Heinrich A. Berntusen, Germany. (Badische.) 
Bluish-red dye and process of making same. Sulfonated rhodamin. 

Diethyl benzyl RHODAMIN warmed on water bath in conc. H,SO, soln. diluted, pptd. with 
soda, etc. Or RHODAMIN is dissolved in fuming sulf. (30 per cent anhyd.) below 10°. Rep 


basic and basic mordant dye. 
Near S. 58:1—‘‘Fast Acid Eosin G.” 


646,794—Apr. 3, 1900. Heinrich A. BERNTHSEN, Germany. (Badische.) 
Acid rhodamin dye and process of making same. Rhodamin anilid, sulfo acids. 


Tetra ethyl RHODAMIN, derived from phthalic acid, is condensed with ANILIN to form a 
rhodamin anilid, which is sulfonated in 5 parts fuming H,SO, (23 per cent SO,) at 100°. Rep 
acid dyes, fast to light. 


649,716—May 15, 1900. Hermann BorpreKxer, Germany. (Hochst.) 
Sulfonated dichlordiethylrhodamin and process of making same. 


Dichlor FLUORESCEIN and ETHYL amin together with ZnCl, and CaO are heated at 200°, 
melt pulverized and purified by extraction with hot dil. HCl, and product sulfonated in 6 parts 


GROUP XIX.—XANTHONE 309 


sulf. monohydrate at 40° to which equal parts fuming H,SO, (20 per cent SO,) are added. 
Violet RED acid dye. 


656,426—Aug. (21, 1900. Albrecht Scumipt, Germany. (Héchst.) 
Rhodolalkyletherester. Rhodol alkyl ether alkyl esters. 

Diethyl rHopoL and DIMETHYL sulfate are mixed with soda ash and heated at 85-90°. Homo- 
logs and derivs. of both compounds may be used. Orange to violet RED basic mordant dyes. 


675,215—May 28, 1oo1. Carl HorrmMann, Germany. (Hochst.) 
Rhodamin sulfonic acid and process of making same. 

as-Dialkyl RHODAMINS from dialkyl amino oxy benzoyl sBENzorc acid and 3-amino PHENOL, 
are sulfonated in fuming H,50, (35 per cent SO,). Violet rED acid dyes, fast to alkali. 


694,149—Feb. 25, 1902. Carl Horrmann, Germany. (Hochst.) 
Acidyl dialkylrhodamin and process of making same. 

To 2 parts diethyl amino oxy benzoyl BENzoIc acid in 20 parts 66° H,SO, is added 1 part 
3-OXyY ACETANILID and temp. of 20-30° maintained for 4-5 hours. Other components claimed. 
Orange to violet RED basic mordant dyes. 


695,441—Mar. 18, 1902. Johann J. Brack, Switzerland. (Basle.) 
Process of making phthalein dyes. Improved process for as-dialkyl rhodamin esters. 
Instead of first condensing the rhodamin then esterifying, the dialkyl amino oxy benzoyl 
BENZOIC acid is heated at 100° in sulf. acid methyl alc. mixture to form ester and to same mix- 
ture is added 3-amino 4-cREsoL or other at 140-160° to condense to rhodamin ester. Rep basic 
mordant dyes of more violet shade than symmetrical derivs. 
Note 578,578 and 584,119. 


738,227—Sept. 8, 1903. Oscar NastvoGEL, Germany. (Elberfeld.) 
Red dye. Dichlor dialkyl ditolyl rhodamin, or derivs. 
One mol. 2-chlor BENZALDEHYDE is condensed with 2 mols. methyl 3-amino 4-crEsou by re- 


fluxing in 50 per cent alc., product separated and heated at 100° in 87 per cent H,SO,, and 
oxidized with FeCl,, Homologs and derivs. claimed. Red basic mordant dye. 


759,657—May 10, 1904. Augustus BiscHLER, Switzerland. (Basle.) 
Red basic rhodamin dye and process of making same. 

as-Trimethyl RHODAMIN base produced as in 578,578, with equal parts alcohol or glycerin, 
etc. and 0.25 parts chlor acETAMID, is heated to 130°. Alkylated chlor acetamid, chlor acetic 
ethyl ester or other halogenated fatty acid may be used. Rep bas‘c dyes. 


821,452—May 22, 1906. Heinrich A. BeRNtHSEN, Germany. (Badische.) 
Rhodamin dye and process of making same. Monoalkyl rhodamins. 

PHTHALIMID and equimol ethyl 3-amino PHENOL with about equal parts boric acid are heated 
at 150-160° and powd. melt boiled in dil. NaOH till NH, ceases to evolve. The separated ethyl 
amino oxy benzoyl benzoic acid is dissolved in 96 per cent H,SO,, 1 mol. acetyl 3-amino PHENOL 
added and temp. held at 20-30° for 6 hours. Other similar components claimed. Rep basic 
and basic mordant dyes of more orange shade than more highly alkylated rhodamins. 

Note 499,927 and 516,584. 


913,514—Feb. 23, 1909. Walter Konic, Germany. (Bayer.) 
Red dye. Chromophor (CH,), N-C’-C’-C=C’-C’/=N-, last N being part of indole ring. 
2'.4'-Dinitro phenyl PYRIDINIUM chloride or other, heated in alc. soln. with dihydro methyl 
INDOLE, then poured into dil. HCl. Pyridin ring splits at nitrogen, forming alifatic aldehyde. 
Dinitranilin partly splits off during reaction and is removed by dissolving in hot aq. and repptg. 
by HCl. Rep basic mordant dyes, faster to light than Rhodamin 6 G. 
Note 913,514, 947,918 and 949,906. 


, 


913,514—Feb. 23, 1909. Walter K6nic, Germany. (Bayer.) 


Red dye. 
Pyripin or deriv. is mixed with methyl] PHENMORPHOLIN OF deriv. in methyl alc. soln. and 
CNBr in ether soln. slowly added then excess HCl. Other diluents or aq. solns. may be used.° 


Rep to vioLeT basic mordant dyes, fast to washing and light. 


310 DIGEST OF PATENTS 


947,918—Feb. 1, 1910. Walter Konic, Germany. (Bayer.) 
Red basic dye. 

Dihydro indole or derivs. condensed with aldehydes, or derived oxims or hydrazones, hav- 
ing the nucleal formula NH,.CH=CH-CH—C-CHO, in which one H of the amino group is re- 
placed by an aryl deriv. and any or all of the other H atoms by alkyl. or other substituents. 
YELLOW to RED basic mordant dyes fast to washing and light. 

Note 913,513. 


949,906—Feb. 22, 1910. Walter Konic, Germany. (Bayer.) 
Yellow to red basie dyes. 


Patent is similar to 947,918 except that PHENMORPHOLIN or derivs. are employed in place 
of dihydro indoles. Rep to vioLetT* basic mordant dyes, fast to washing and light. 


990,224—Apr. 25, 1911. Arnold Brunner, Germany. (Hochst.) 
Fluorescein dyestuff and process of making same. Fluoresceins resembling more 
expensive iodin or bromin derivs. containing chlorin in resorcinol nucleus. 
Dichlor fluorescein, from chlor RESORCINOL and PHTHALIC acid, is suspended in alc. and Br 
or I added.- Rep acid dyes similar to Erythrosin. 


1L,002,825—Sept. 12, 1911. Charles pe LA Harpe and Ernest Bopmer, Switzerland. (Basle.) 
Red mordant dyestuff and process of making same. Sulfonated dimethyl rhodol. 

Resorcin sulfo acid and dimethyl amino 3-oxy benzoyl BENzorc acid or derivs. are heated 
at 90° in 70 per cent H,SO,. Orancer to violet REp acid or acid mordant (Cr) dyes, fast to 


Cl and light. 
Note 1,003,257. 


1,003,257—Sept. 12, 1911. Charles p—E 1A Harpr and Ernst Bopmer, Switzerland. (Basle.) 
Violet mordant dyestuff and process of making same. Sulfonated oxy dimethyl 
rhodol. 
Process is same as in 1,002,825 using PYROGALLOL sulfo acid for resorcinol deriv. WVu1oLEt 
acid and acid mordant (Cr) dyes, fast to light, fulling and S. 


1,006,738—Oct. 24, 1911. Wilhelm EmmMeEricu, Germany. (Hdéchst.) 
Red acid dyestuff of the triphenylmethane series and process of making 
same. Classed by patent as triphenyl methane dye but should be with xanthones. 
BENZALDEHYDE 2.4-disulfo is condensed by boiling in dil. acid soln. with dimethyl 3-amino 
PHENOL and ethyl amino cresou, dried, then heated in conc. sulf., to close pyrone ring. Rep 
acid dye. 


1,054,247—Feb. 25, 1913. Arnold Sterner, Switzerland. 
Manufacture of dyes of the cerulein series. (Product also claimed.) Diethylamino 
oxy cerulein. 

PuTHALEIN obtained from diethyl amino 3-oxy benzoyl BENzorc acid and PYROGALLOL is 
heated slowly to 155-160° in 1o parts 96 per cent H,SO, Weak fuming acid causes quicker 
condensation. Other methods and components given. GREEN to BLUE acid mordant (Cr) or 
basic mordant (tannin) dyes, fast to light on Cr mordant, easily sol. and adapted for printing. 


1,055,864—Mar. 11, 1913. Ernst BopMeEr and Charles pk tA Harpe, Switzerland. (Basle.) 
Yellow to red mordant dyestuffs and process of making same. Nitro rhodols. 

Dimethyl rHopor sulfo acid, or other, prepared as in 1,002,825, is dissolved in 4 parts conc, 
H,SO, at usual temp., more acid containing one mol. HNO, is added, and let stand several days 
or ned a short time at 70°. YELLOW to RED acid mordane (Cr). dyes, faster to light than 


non-nitrated dyes. 
1,055,885—Mar. 11, 1913. Charles p— 1A Harpe and Ernst Bopmer, Switzerland. (Basle.) 
Orange-red to bluish-red mordant dyestuffs and process of making same. 


Nitro rhodols. 
Resorcin is sulfonated in 11 parts conc. H,SO,, then nitrated to nitro REsorciN disulfo and 
to the mixture is added 1 mol. dimethyl amino 3-oxy benzoyl BENzoIc acid or an equivalent comp. 


* Note that in claims dyeings are said to be yellow to red, which differs from body of patent. 


GROUP XX.—MINERAL DYES ay 


and temp. kept at 90°. Nitro REsorcyLic acid or similar comps. may be used for condensation. 
ORANGE to violet RED acid mordant (Cr) dyes. 
Note 1,002,825. 


1,106,185—Aug. 4, 1914. Ernst BopMER, Switzerland. (Basle.) 
Green mordant dyestuffs and process of making same. Sulfonated rhodols or 
ceruleins from pyrogallol sulfo acids. 


Ruopo. sulfo acid, obtained from diethyl amino 3-oxy benzoyl BENzoIc acid and PYROGALLOL 
disulfo, is added to 4 parts fuming H,SO, (20-25 per cent SO,), and heated to 150-155°. Other 
components are claimed and table of reactions given. Sufficient SO, must be present to com- 
bine with all water formed, GREEN acid mordant (Cr) or basic mordant (tannin) dyes fast on 
cotton to washing, soap, Cl and light and on wool to fulling and light, adapted for printing. 


1,194,380—Aug. 15, 1916. Hans GAcENBACH, Switzerland. (Basle.) 
Phthalein dye and process of making the same. Naphtho xanthone derivs. 
1’-Oxy 2/-naphthoyl 2-BENzoIc acid or deriv. is condensed with equimols PYROGALLOL by 


heating at 80° in 5 parts 75-85 per cent H,SO, Or ZnCl, can be used as condensing agent. 
BuivE (Cr) to GREEN (Cr) acid mordant dyes. 


1,381,503—June 14, 1921. Alfred IL. Rispier, Missouri. (Monsanto.) 


Process of producing phthaleins. Phenolphthalein dyes of high yield and purity pro- 
duced at low temp. 


PuTHALic anhyd. and 2 parts PHENOL are heated dry to 80° then from 2-2.5 parts an- 
hydrous aromatic sulfo acid added and temp. kept at 120° for 10-12 hours. Anhyd. ZnCl, can 
be added to mass to promote the reaction, and correspondingly less sulfo acid. HCl will distill 
off and carry away HO. 90 per cent yield claimed. Rep dye used for indicator and medicine. 


1,403,888—Jan. 17, 1922. Manfred AtiotH and Ernst BopMeEr, Switzerland. (Basle.) 
Dyestuffs dyeing on mordant and process of making same. Dianilino tri sal- 
icyl phthalein. 

Anilino saLicyLic acid is condensed with para FORMALDEHYDE in 66° H,SO, at usual temp., 
another mol. saticyLic acid is added and mass oxidized by HNO, (NaNO, added) at 30-50°. 
Separated dye is then sulfonated in 66° H,SO, at 90-95°. Anilino cresotinic acid or any ortho 
oxy carbo acid or other methylene di-anilino 2-oxy carbo acid may be used. Rep acid mordant 
(Cr) dyes of good fastness. 


ALLIED COMPOUNDS. 
Group XX.—MINERAL DYES. 


BLUEING. 

64,897—May 21, 1867. . George A. Moss, New York. — 
Improved box for blueing and other powders. 
72,817—Dec. 31, 1867. James H. Ditxs, New York. (Raynolds.) 
Tmproved lump blue for use in laundries and in bleaching. 
72,818—Dec. 31, 1867. James H. Ditxs, New York. (Raynolds.) 
Improved process of making soluble blueing for use in laundries and 

bleaching. 
76,935—Apr. 31, 1868. Edward L. Moringux, New York. 


Improved method of preparing laundry-blueing. 


155,239—Sept. 22, 1874. James Jackson, Illinois. 
Improvement in bluing-powders for laundry use. 


181,282—Aug. 22, 1876.:. aT - Thomas S. Rozinson, New York. 


Improvement in liquid laundry-bluing. 


312 


208,180—Apr. 30, 1878. 


DIGEST OF PATENTS 


Charles H. Fiscner, New York. 


Improvement in laundry-bluing packages. 


210,808—Dec. io, 1878. 
Improvement in bluing-packages. 


236,634—Jan. 11, 1881. 
Granulated laundry-bluing. 


251,384—Dec. 27, 1881. 
Bluing-paddle. 


259,832—June 30, 1882. 
Disinfectant laundry bluing. 


302,544—July 29, 1884. 
Bluing-paper. 
303,144—Aug. 5, 1884. 


Laundry-bluing. 


326,601—Sept. 22, 188s. 
Compound for laundry bluing. 


351,484—Oct. 26, 1886. 
Soluble laundry-blue, 


384,804—June 19, 1888. 
Bluing-paper. 


396,417—Jan. 22, 1880. 
Dye. 


399,974—Mar. 19, 1880. 
Bluing-package. 


426,504—Apr. 29, 1890. 
Laundry-blue. 


553,556—Jan. 28, 18096. 
Laundry-blue. 


738,481—Sept. 8, 1903. 
Effervescent laundry bluing. 


804,798—Nov. 14, 1905. 
Laundry-blue distributer. 


824,294—June 26, 1906. 


Laundry-blue. 


826,567—July 24, 1906. 
Laundry bluing. 


846,887—Mar. 12, 1907. 
Effervescent laundry bluing. 


1,219,186—Mar. 13, 1917. 
Laundry bluing. 


1,224,737—May 1, 1917. 
Process of producing laundry blue. 


Charles R. Grorr, Minnesota. 


Henry Sawyer, Massachusetts. 


Henry Sawyer, Massachusetts. 


Archelaus E. Spencer, Illinois. 


Daniel Dunscoms, New York. 

George A. Conant, Massachusetts. 
Charles Franke, New York. (Hoffman.) 
Payton Spence, New York. 

George W. Bartow, New York. 

George H. Wetss, Massachusetts. (Carter.) 
Sylvester M. Nevius, Ohio. 

Theodore F. Conxuin, Illinois. (Lapperr, %.) 
G. R. B. Kempton, England. 
James W. Fu.iier, Minnesota. 


William C. Port, Missouri. 


Patrick Dramonp, Pennsylvania. 


Robert G. GriswoLtp and William T. Donovan, Massachusetts. 


(Laundry Blue.) 


Elizabeth S. Yarnatu, Missouri. 


Adrianna Sturcxe, New York. 


George F. Griuipatrick, Missouri. (Devoe.) 


Ee ee oe he 


GROUP XX.—MINERAL DYES 313 


OTHER THAN BLUEING. 


441—Oct. 28, 1837. Henry StepuHens, England. 
Manufacture of coloring-matter, 


441—Oct. 28, 1837. Reissue, 3—Apr. 21, 1838. Henry SrerpHeENs, England. 
Improved manufacture of coloring-matter, 


9,890—July 26, 1853. Frederick G. Verrercxe, New York. 
Dyeing compound. 


87,270—Feb. 23, 1860. Anton LeyKaur, Bavaria. 
Improvement in the manufacture of colors. 


88,291—Mar. 30, 1860. Eberhard Harrscu, New York. 
Improvement in the manufacture of colors and pigments. 


88,793—Apr. 13, 1869. Joseph Lory, Tennessee. 
Improved hair-dye. 


90,359—May 25, 1860. Eberhard Harrscu, New York. 


Improvement in the manufacture of colors. 


202,822—Apr. 23, 1878. Reinhold Horrman, Germany. 


Improvement in manufacture of ultramarine colors. 


207,093—Aug. 13, 1878. Johann ZELTNER, Bavaria. 


Improvement in manufacture of red ultramarine. 


207,836—Sept. 10, 1878. Johann ZELTNER, Bavaria. 
Improvement in manufacture of violet ultramarine. 


213,189—Mar. 11, 1879. Leopold Grar, New Jersey. 
Improvement in the manufacture of prussian blue. 


562,045—June 16, 1896. Maria A. Stevens, Minnesota. 
Composition of matter for coloring fabrics. 


611,870—Oct. 4, 18098. Theron C. Srearns, New Jersey. (Kellogg.) 
Dyeing hair or fur. 


629,231—July 18, 1899. Johannes C. Boot, New York. 
Process of dyeing hair. 


693,703 
Ferrochrome color and process of making same. 


Feb. 18, 1902. Albert Haacen, Germany. 


1,332,974—Mar. 9, 1920. Charles H. Dennison, Massachusetts. (Amer. Rubber.) 
Method of coloring fibrous material. (Product also claimed.) 


1,332,982—Mar. 9, 1920. Willis A. GisBons, New York. (Amer. Rubber.) 
Method of coloring fibrous material. (Product also claimed.) 


1,361,139—Dec. 7, 1920. Clarence I, Coir, Arkansas. (Cole.) 
Method of dyeing and preserving fabrics. Preserving canvas, yarns, etc. from mil- 
dew by copper tannate. 
Fabric is treated with 2 per cent Tannic acid then with 5 per cent CuSO, soln. containing 
65 per cent CaCO, in suspension. ' 


314 DIGEST OF PATENTS 


Group XXI—VEGETABLE AND PETROLEUM DYES. 


(Patents for preparation of madder and natural indigo for dyebaths are 
included with Group XXIII Applications, Subgroups III and VII.) 


VEGETABLE DYES. 


66,897—July 16, 1867. Gustav A. SrrcLE, New York. 
Improved method of manufacturing carmine. 


76,107—Mar. 31, 1868. Dr. Charles SztrpEL, New York. 
Improved vegetable coloring-matter. 


81,992—Sept. 8, 1868. C. E. Fox and Mary E. Fox, California. 
Improved dye-stuff, 


109,489—Nov. 22, 1870. Spencer BorpEn, Massachusetts. 
Improvement in the preparation of garancine. 


167,360—Aug. 31, 1875. John S. SELLton and Robert Pinkney, England. 
Improvement in dyeing and printing. 


203,140—Apr. 30, 1878. Leopold Grar, New York. 
Improvement in dyestuff or coloring matter. 


221,381—Nov. 4, 1879. Morris Wist, New York. (Wise.) 
Improvement in the preparation of dye-stuffs, 


240,467—Apr. 19, 1881. — Gustav ScHWARZWALD, New York. 
Composition for printing textile fabrics. 


320,526—June 23, 1885. Charles E. Avery, Florida. 
Process of preparing logwood extract. 


329,125—Oct. 27, 1885. Adolf T. B6umeE, Germany. 
Process of making coloring matter. 


356,368—Jan. 18, 1887. Jean A. Marutev, Maryland. 


Manufacture of dyestufis. 


443,026—Dec. 16, 1890. Franz C. Werss, Austria-Hungary. (Klimosch, %.) 
Dye. 


458,244—Aug. 25, 1891. Josiah S. Tyrer, Washington, D. C. 


Litmus pencil. 


491,972—Feb. 14, 1893. Peter T. Austen, New Jersey. (Matheson.) 
Coloring-matter from logwood and mode of preparing same, 


492,368—Feb. 21, 1893. Peter T. Austen, New Jersey. (Matheson.) 


Solid coloring-matter from fustic and process of preparing same. 


493,286—Mar. 14, 1803. Charles F. X. Noroy, France. 
Process of dyeing black. 


' §42,403—July 9, 18095. Peter ft. AUSTEN, New York. (Matheson.) 


Proeess of making coloring-matter from logwood. 


633,243—Sept. 10, 1899. Leon P. Marcuiewsk1, E. S. Witson and E. Stewart, England. 


Process of making dyes. 


640,061—Dec. 26, 1899. E. S. Witson and EF. Stewart, England. 
Dye from cottonseed oil. 


ek ee 


GROUP XXI.—VEGETABLE AND PETROLEUM DYES ars 


683,786—Oct. 1, 1901. Thomas Newsome, Massachusetts. (Amer, By-) 
Dye from cottonseed and method of making same. 


704,843—July 15, 1902. Roberto Leretir and Ernesto Tacurant, Italy. 
Process of making extract dyes. 


759,008—May 3, 1904. Francis J. Oaxes, New York. 
Glucoside dye and process of making same. 


763,616—June 28, 1904. George McC. Lawton, Massachusetts. 
Dyeing composition. 


768,809—Aug. 30, 1904. George McC. Lawton, Massachusetts. 
Dyeing composition. 


872,250—Nov. 26, 1907. Francis J. Oaxres, New York. 
Dyestuff and process of making same. 


8$94,965—Aug. 4, 1908. Frederick J. Maywatp, New York. 
Friable vegetable dye and process of making same. 


954,949—Apr. 12, 1910. Gilbert J. Fowxer, England. 
Process of extracting lac dyes. 


1,031,602—July 2, 1912. Marcus WECHSLER, England. (Gillman.) 
Method of producing organic coloring-matter. 

1,185,605—May 30, 1916. John Purinc, New York. (Robeson.) 
Leather dyes. 

1,193,838—Aug. 8, 1916. William SomeErviLie, Australia. 
Dye or stain. 

1,222,433—Apr. 10, 1917. Edith O’N. Macponatp, New York. 
Dye composition. 

1,243,042—Oct. 16, 1917. William W. Cok, Jr., England. 
Dye. 

1,254,914—Jan. 29, 1918. Isidor Krrstr, Pennsylvania. 


Vegetable dye and method of preparing the same. 
1,266,577—May 21, 1918. John W. Frits, North Carolina. 
Composition for use in dyeing. 

1,273,293—July 23, 1918. Herbert Warxurp, New York. (Young.) 
Vegetable dye and process of making same. 

1,306,710—June 17, 1919. Hiroshi Nomura, Japan. 
Method of extracting a pungent principle from ginger root. 
1,283,296—Oct. 29, 1918. John Purinc, New York. (Robeson.) 
Direct dyeing. 

1,821,973—Nov. 18, 1919. Charles Otto Bouz, Virginia. 
Art of dyeing. 

1,330,992—Feb. 17, 1920. Rafael H. Vecas and Marcelino H. Vecas, Argentina. 
Coloring product and tinctorial mordant. 

1,362,879—Dec. 21, 1920. Alice M. Hart, England. 


Process of preparing a dye base. 
et 


316 DIGEST OF PATENTS 


1,367,862—Feb. 8, 1921. Albert L. Capp, Massachusetts. (Metalite.) 
Dye substitute. 


1,368,456—WNov. 9, 1920. Walter J. Mrtuer, Minnesota. 
Dye compound. 


1,386,166—Aug. 2, 1921. Edouard pk GroussEAu and Auguste Viconene, France. 
Treatment of cocoa waste. 


1,386,201—Aug. 2, 1921. Oscar LL. Prrerson, Connecticut. 
Speck-dye composition. 


1,399,014—Dec. 6, 1921. Eady Hart, Australia. (Stewart.) 
Dyestuff and mode of producing it. 


PETROLEUM DYES. 


518,989—May 1, 1894. Hans A. Frascu, Ohio. (Grasselli.) 
Petroleum sulfo-acid. (Process also claimed.) 

Crude petroleum, distillates or products, is sulfonated and 2 soluble products separated by 
solubility of calcium salts, using soluble portion, called “alfa”? acid. YrtLow (green fluor) 


acid dye that can be diazotized on fiber. 
This is free dyestuff acid of 518,992. Sce also 518,990. 


518,990—May 1 1894. Hans A. Frascu, Ohio. (Graselli.) 
Petroleum sulfo-acid. (Process also claimed.) 

Petroleum is sulfonated in fuming H,SO, at ordinary temp. the 2 soluble sulfo products 
dissolved out, and alfa separated from beta comp. by solubility of its calcium salt, the beta or 
insol. portion being claimed. Brown, fluor. acid dye that can be diazotized on fiber. 

Addition to 518,989. 


518,991—May 1, 1894. Hans A. Frascu, Ohio. (Grasselli.) 


Brown petroleum nitro dye. (Process also claimed.) 
PETROLEUM, crude or distillates, is nitrated and sulfonated (probebly) by mixed acids, 
and two products separated as Ca salts (Ba or Pb also) using soluble portion. Red srown, 


(blue-green fluorescence) acid dye. 
Note 519,036 for use of portion the Ca salt of which is insoluble. 


518,992—May 1, 1894. Hans A. Frascu, Ohio. (Graselli.) 


Petroleum dye. (Process also claimed.) 

Crude PETROLEUM, distillates or products, is sulfonated, soluble Ca salt prepared as in 
518,989, and salted out to form alkaline salt or dye. Patent is apparently the alk. salt of 
518,989 claims being made for a yELLow acid dye whereas former patent claims a sulfo acid 
capable of dyeing yellow in acid soln. 


519,036—May 1, 18094. Hans A. Frascu, Ohio. (Graselli.) 


Brown petroleum dye. (Process also claimed.) 

Crude PETROLEUM, distillates or products, is heated with mixed acids till soluble, prods. 
separated as calcium salts using the insoluble calcium salt. Process is same as in 518,991, but 
claims the Ca salt of a nitro acid that is insol. in aq. and which gives as free acid a Brown direct 


dye. 


1,308,660—July 1, 19109. Hans A. Frascu, New York. 


Dyestuff. (Process also claimed.) 

Products obtained as in 518,989 and 92 by pptg. sulfo acids of petroleum with lime, etc. 
are added to 10 parts 10 per cent NaOCl, filt., and heated until no more insol. portion forms. 
The soluble part, termed ‘‘Petracin A” is salted cut. Instead of NaOCl, nitro-HCl or equiv. 


may be used. Product is YELLOW acid dye. 


GROUP XXII.—INTERMEDIATES es 


1,323,263—Dec. 2, 19109. Hans A. Frascu, New York. 
Dyestuff. (Process also claimed.) 


This is a co-patent with 1,308,060 and claims the insol. Ca product after oxidation with 
NaOCl, or the so-called “‘Petracin B,’’ which is an ORANGE to BROWN direct dye. 


1,409,083—Mar. 7, 1922. Harry H. Cuumer, Illinois. 
Dye and process of producing dyes. Dyes from bitumens. 


Bituminous substances such as gilsonite, mineral shales, asphalts, etc., are distilled, from 
510° upwards, with or without vacuum or pressures up to 300 lbs., condensed oils extracted with 
acids, or salts, etc., ozonized if desired, concd. and dissolved in appropriate solvent. VARI-COLORED 
alcohol soluble dyes, suitable for wood or paper coloring. 


Group XXII.—INTERMEDIATES. 


Including General processes, Acetic acid and derivatives, Alcohols (synthetic), Chlorhydrins, 
Crudes, Formaldehyde and derivs., Soluble oils, Urea and derivs. 


126,277—Apr. 30, 1872. Henry J. Fenner and Frederick Vrersmann, England. 
Improvement in apparatus for preparing anthracene. 


Combination of tar still with series of pitch retorts and ANTHRACENE receiver, etc. Draw- 
ings of apparatus shown. 


130,909—Aug. 27, 1872. Henry J. Fenner and F. Versmann, England. 
Improvement in the manufacture of anthracene. 


ANTHRACENE is derived from coal tar pitch by regulated distillation at high temps. aided by 
use of partial vacuum, combined with distillation of oils from coal tar by continuous process. 
Apparatus described with drawings. 


131,393—Sept. 17, 1872. Joseph C. F. CuHErtver, New York. 
{mprovement in apparatus for preparing anthracene. 


A still having compartments connected by overflow pipes and condenser for continuously 
separating coal tar pitch from ANTHRACENE, is described with drawings. 


184,142—Nov. 7, 1876. Samuel Casot, Jr., Massachusetts. 
Improvement in processes of manufacturing anthracene. Manufacturing an- 
thracene by injecting into still a vapor of less latent heat than steam. 
Petroleum ethers or other light hydrocarbons vaporized by passing thru pipes, etc. near 
still, are then injected into still to aid distillation of ANTHRACENE or other heavy hydrocarbon. 
Drawings of still, plan and elevation are given. 


210,233—Nov. 26, 1878. Heinrich Baum, Germany. (Hochst.) 
Improvement in coloring-matters to be used as dyes. 2-Naphthol 3.6-disulfo or 
6.8-deriv. 


2-NAPTHOL, 1 part, and sulfuric acid (1,848), 3 parts, are heated at 1o0-105° for 12 hours. 
Sodium salts formed and “G” separated from “R” salt by extraction of ppt. with alcohol. 
Portion insol. in alcohol (R salt) used in patent. 


225,90S8—Mar. 23, 1880. Francois Z. Roussin, France. (Poirrier.) 
Artificial coloring-matter. Naphthionic acid. 


NAPHTHYLAMIN, 1 part, mixed with 4-6 parts H,SO,, (66°), heated to 140°, diluted, filt., 
washed and transformed to alk. salt. 


227,588—May 11, 1880. John J. Ketter, New York, and John R. Gercy, Switzerland. 
Manufacture of anthracene. (Product also claimed.) Anthracene and anthracitic tar 
from petroleum. : 
PrrroLeum or petroleum tar allowed to drip into retorts heated to 400-600° specially 


prepared with coke, coated with lampblack or platinized or with plates of Pt. foil, and vapors 
passed thru water tank to remove tar then into scrubbers. Furnace is described with drawings 


and process given in detail. 


318 DIGEST OF PATENTS 


237,917—Feb. 15, 1881. Z. H. Sxraup, Austria. (Badische.) 
Production of oxychinoline. (Product also claimed.) Oxy quinolin. 
2-Nitro PHENOL mixed with 1.5 parts 2-amino PHENOL about 4 parts GLYCERIN (1.26) and 
3-5 parts conc. H,SO, (1.85) refluxed below 150° for 2 hours, excess nitrophenol removed by 
steam and product pptd. by alkali. It may be used for making blue dyes. 
Note 237,918 for same process using para nitro phenol. 


237,918—Feb. 15, 1881. Z. H. Sxraup, Austria. (Badische.) 
Production of oxychinoline. (Product also claimed.) Oxy quinolin by new process. 
4-Nitro PHENOL mixed with 1.5 parts 4-amino PHENOL about 4 parts GLYCERIN (1.26) and 
3.5 parts conc. H,SO, (1.85) refluxed 2 hours below 150°. 
Note 237,917. 


241,7238—May 17, 1861. Zdenko H. Sxraup, Austria. 
Manufacture of artificial chinoline. (Product also claimed.) Synthetic quinolin, 
b.p. 236.7-237.7°. 
Nitrobenzene is mixed with ANILIN and GLYCERIN (1.26) to which conc. sulf. acid (1.848) 
is added, stirred till clear then refluxed till all nitrobenzene has entered thc reaction, the last 
traces of this removed by steam and quinolin pptd. by alkali. 


246,272—Aug. 23, 1881. - H. Baum, Germany. (Hochst.) 
Azo coloring-matter. 2-Naphthol mono sulfo, Na salt. 

NaPHTHOL heated not ahove 25° with 3 parts H,SO, (1.84), diluted. neut. with milk of 
lime and converted to Na salt. 


251,163—Nov. 22, 1881. H. Baum, Germany. (Ho6chst.) 
Manufacture of crimson coloring-matter. 2-Naphthol 3.6- and 6.8-disulfo acid, 
sodium salts (“‘R’ and “G”’ salts). 
2-NAPHTHOL heated in 3 parts conc. sulfuric at 100—110° for 12 hours, and two isomers 
separated by digestion in 3-4 parts alcohol in which ‘‘R” salt is insol. 


252,782—Jan. 24, 1882. Adolf LresmMann, Germany. 


Manufacture of the higher homologues of phenol, naphthol and resorcin. . 


Components for dyes, disinfectants, salicylic acid, ete. 
PHENOL or other, is condensed with ZnCl, in amyl alcohol, methyl, benzyl, or other alcohol 
to form higher homologs. 


256,330—Apr. 11, 1882. Edward D. Kenpati, New York. 
Process of treating certain derivatives of coal-tar products. Reducing nitro 
compounds. 


NITROBENZENE, nitro toluene, or other nitro body is reduced in acid soln, by electrolysis 
to anilin etc., (apparatus described). .Further electrolysis produces dyes of various colors. 


256,381—Apr. 11, 1882. Carl Rumprr, Germany. 
Manufacture of a new color-producing acid. (Product also claimed.) 2-naphthol 
a-sulfo (position of sulfo group not shown but probably 8.) 
2-NAPHTHOL heated with com’l. (66°) sulfuric below 60° to form two isomers. The alfa sulfo 
isomer of patent is separated from beta by the soln. of its Na salt in 90 per cent alc. Prod- 
uct compared with other sulfo acids. 


256,400—Apr. 11, 1882. James H. Sressins, Jr., New York. 
Production of naphthyl-sulphate soda salt. 
2-NAPHTHOL sulfonated in 3 parts conc. H,SO, (1.84), below 20°, and sodium salt of NAPI- 


turyL sulfate separated from 2-naphthol sulfonate by hot alcohol. 
Note 256,401 for use of above. 


262,680—Aug. 15, 1882. Friedrich Mann, New York. (Schoellkopf.) 
Manufacture of rosanilin color, Ethylene disulfo acid or “Ethionic” acid. 


Vapors of sulfuric acid are conducted into anhyd. alcohoi or dried ETHYLENE gas is passed 
into liquid sulfuric or mixed with vapors of sulfuric acid to form ‘‘Carbyl sulfate,’ (or the 
anhydride of ‘“‘Ethionic’” acid) then water is added or not. 


P — a 


GROUP XXII.—INTERMEDIATES 319 


268,505—Dec. 5, 1882. C. F. L. Limpacu, Germany. (Hochst.) 
Manufacture of coloring-matter. (Product, not process, claimed.) 2-Naphthol tri- 
sulfo. 


2-NAPHTHOL heated in 4-5 parts fuming H,SO, (20 per cent SO,) to r140-160° until a 
sample with NH, gives a soln. with green fluor. which couples with diazo xylidin in alk. soln., 
then product is converted to Na salt. 

Note 268,506 and 507 also give mfr. of above—Group VI. 


268,543—Dec. 5, 1882. Christian Rupotpu, Germany. (Hochst.) 
Production of methylquinoline. (Product also claimed.) Methyl quinolin. 


BENZYLIDENE acetone is nitrated at o-15°, diluted, filt., washed and ortho separated from 


para mono nitro deriv. by soln. in alcohol, then resulting 2-nitro BENZYLIDENE acetone reduced, 
preferably by SnCl, and HCI. 


270,045—Jan. 2, 1883. Otto FiscuEr, Germany. 
Method of preparing oxyquinoline. 


QuINOLIN sulfo acid is carefully fused in open pan with 1-2 parts NaOH or 2-3 parts KOH. 


275,128—Mar. 3, 1883. Julius BrONNER, Germany. 


Method of purifying impure anthrachinone and alizarine. Purifying anthra- 
quinone and alizarin, and apparatus therefor. 


ANTHRAQUINONE, crude, analyzed to determine amount of impurities, mixed with from 2.5 
to 3 parts solvent naphtha, in a continuous extraction apparatus, solvent being recovered con- 
tinuously, insol. impurities being removed by filtration and anthraquinone continuously recov- 
ered by being crystallized fractionally from naphtha soln. and removed by filtration. Drawing 
and description of apparatus given. 


277,864—May 15, 1883. Hermann EnpemMann, New York. (Pickhardt.) 


Production of sulpho-acid compound of betanaphthol. (Product, not process, 
claimed.) 2-Naphthol sulfo. 


2-NAPHTHOL dissolved in 4 parts H,SO, (1.85) at 26° then temp. allowed to rise to 115-125°, 
cooled to 110° and fuming H,SO, added. Test for end of reaction given. 


278,926—June 5, 1883. Eugen Fiscuer, Germany. (Hochst.) 
Production of paranitrobenzylidene chloride. 4-Nitro benzylidene chloride. 


4-Nitro TOLUENE, pure cryst., is heated on oil bath to 130° and while raising gradually to 
160° CHLORINE gas passed in until definite increase of weight, separated and cryst. from alc. May 
be converted to 4-nitro BENZALDEHYDE by sulf. aeid, HCl being evolved. 


280,317—June 26, 1883. Leonard Limpacu, Germany. (Hochst.) 
Manufacture of intermediate. (Product also claimed.) 2-Naphthol trisulfo. 


2-NAPHTHOL, mono or disulfo acid, sulfonated in H,SO, (20 per cent SO,) at 140-160°. Test 
for end of reaction given. Mono chlor hydrin and sulfuric can also be used. 


282,835—Aug. 7, 1883. August BerntusEN, Germany. (Badische.) 
Manufacture of materials suitable for dye-stuffs. (Product, not process, claimed.) 
Thio diphenylamin. 


DIPHENYLAMIN and sulfur are heated at 250-300° till H,S ceases to evolve, then purified by 
distillation and crystn. from alc. This is product patent for process 286,526. Note also 282,836. 


286,526—Oct. 9, 1883. August BerntHsEN, Germany. (Badische.) 


Sulphureted derivative of diphenylamin as a basis for the production of 
coloring matters. (Process, not product, claimed.) Thio diphenylamin. 


DIPHENYLAMIN is treated with sulfur at 250-300°. Process for 282,835. 


289,613—Dec. 4, 1883. O. Brent, Germany. 
Manufacture of red coloring-matter. Naphthionic acid. 


NaPHTHYLAMIN is heated to 120° with 5 parts conc. H,SO, until a stiff grayish white mass 
is formed, product filt., and washed to remove excess H,SO, Both alpha and beta naphthyl- 
amin derivs. are formed. 


320 DIGEST OF PATENTS 


309,935—Dec. 30, 1884. Oscar Dorsner and Wilhelm von MituEr, Germany. (Schering.) 
Manufacture of bases called chinaldines. (Product also claimed.) Quinaldin, 
C.,HN,. b.p. 240°, 
ANILIN or other, is condensed by boiling with 1.5 parts PARALDEHYDE in HCl soln. with 
AICl,, poured into aq., filt., pptd. by alk. and fractionated to purify. Other components claimed. 


310,155—Dec. 30, 1884. Leo Vienon, France. 
Sulpho-alpha-naphthol coloring compound. - 1-Naphthol mono sulfo. 


I-NAPHTHOL mixed with H,SO, mono hydrate below 25° until reaction is complete or heated 
at 80° for 3 hours; or fuming H,SO, (20 per cent SO,) may be used in the mixture. 


315,932—Apr. 14, 1885. Robert GNEHM, Switzerland. (Basle.) 
Production of chlorinated derivatives of benzaldehyde. 
BENZALDEHYDE containing some iodine mixed with SbCl,, is kept at 100° till evolution of 


HCl ceases, diluted and extracted with ether, or HCl added to dissolve Sb comps. and benz-~ 
aldehyde deriv., separated as oily layer, purified as bisulfite comp. 


316,248—Apr. 21, 1885. Oscar DorBNER and Wilhelm von MILER, Germany. 
Formation of methoxy and ethoxy chinaldine. 


QUINALDIN or homolog, heated in fuming H,SO, at 1to0-150° according to whether ortho 
or para (lower temp.) or meta (higher temp.) products are desired and three isomers separated 
by solubility in aq. The separated Na salts are fused in 4 parts NaOH and resulting oxy comp. 
converted to alkyl oxy by treatment with iodides or chlorides of alkyl. Or alkoxy derivs. can 
be formed directly from an amino oxy comp. and acetaldehyde boiled with AIC1,. 

Note 309,035. 


316,249—April 21, 1885. Oscar DorBNER and Wilhelm von MILieErR, Germany. 
Formation of the hydrobase of chinaldine. (Product, not process, claimed.) 
QUINALDIN or oxy quinaldin and alkyl derivs. obtained as in 309,935 and 316,248 are boiled 


with Sn and conc. H,SO, several hours, freed from Sn, separated by NaOH and distilled. 
With benzotrichloride gray dyes may be obtained. 


322,368—July 14, 1885. Robert GNEHM, Switzerland. (Basle.) 
Production of chlorophthalic acid. Tetra chlor phthalic acid anhydride. 


Anhydrous PHTHALIC acid is treated at 200° with chlorine in presence of SbCl, distilled 
off and recovered SbCl, reused. 


329,634—Nov. 3, 1885. Emil ELsarsser, Germany. 
Red dye-stuff or coloring-matter. 2-Naphthylamin 5-sulfo, or, ““Dahl’s” acid, purified. 


2-NAPHTHYLAMIN sulfonated by 3 parts fuming H,SO, at 75°, sulfo acid of patent (2.5) 
being extracted by alc. from Na salt of three sulfo acids formed, further purified by pptn. with 
HCl from aq. soln., Ba salts formed, small amt. of insol. ppt. filtered off, and the remaining sol. 
Ba salt of desired acid transformed to Na salt. 


331,059—Nov. 24, 1885. Meinhard HorrmMann, Germany. (Cassella.) 


Manufacture of beta-naphthol sulphonic acid. (Product also claimed.) 2-Naph- 
thol-6.8-disulfo, ‘‘Gamma.” . 


2-NAPHTHOL, treated with 66° sulfuric at 40-60°, and temp. maintained till melt is thick; 
or b) 2-NAPHTHOL sulfo heated in conc. H,SO, at 40-60° for 5-6 hours (or 8-10 days at 20°). 
Quantity and strength of acid, temp., and duration of operation, may be varied reciprocally to 
produce same compound. Purified by coupling mono sulfo impurities with diazo bodies, etc. 

For other sulfo acids, see 210,233 (Baum); 268,506 (Simpach); and 277,863 (Endemann). 


we eee eee ee 


A Pe ee eT ee 


332,358—Dec. 15, 1885. Eugen OsTERMAYER and Max Ditrmar, Germany. 
Producing chloriodine double combinations from pyridine and chinoline 
bases. Chloriod quinolin. 
Cuioriop HCl, (ICI].HCl) formed a) by passing Cl into water containing iodin in soln. or 
suspension, b) by treating iodine compound (KI) with HCl! and nitrite or other combination to 
release Cl, is mixed with QUINOLIN, pyridin, or other, and diluted. 


GROUP XXII.—INTERMEDIATES 321 


332,829—Dec. 22, 1885. Hugo Prinz, Germany. (Bronner.) 
Manufacture of beta-naphthylamine sulpho-acid. 2-Naphthylamin-6-sulfo. 
2-NAPHTHOL sulfo NH, salt (by method of Schaefer) heated under pressure in autoclave at 
180-200° in aq. soln. containing Ca(OH), or other alk. agent. Properties of sulfo acid given. 
S. 172—“Fast Brown,” 174—‘‘Double Scarlet G,’? 176—“‘Double Scarlet ext. S,” S. 172, 
etc. gives the above coupled with 1-naphthol, etc. while patent claims only the intermediate. 


333,034—Dec. 22, 1885. 
Heinrich VoiuBrecuHt and Carl Mrenscuine, New York. (Schoellkopf.) 
Manufacture of color-producing acids. (Product, not process, claimed.) 1-Naphthol. 
4.8-disulfo ‘‘Schoellkopf’s acid.” 

NAPHTHALENE 1-sulfo lime salt is mixed with 2 parts H,SO, (66°), and sufficient HNO, 
added at 90-100°. The two resulting nitro sulfo acids are converted to their amino derivs. and 
the salts of these separated by their unequal solubility in aq. The naphthylamine sulfo acid least 
sol. in aq. is diazotized, boiled in a large amt. aq. to form naphthol sulfo then further sulfonated 
in 2-3 parts H,SO, (66°) at 80-90° until mass is entirely sol. in aq. 


333,040—Dec. 22, 1885. 
Heinrich VoLiBreEcHt and Carl Mrenscuinc, New York. (Schoellkopf.) 
Alphanaphthosulphonie acid.  1-Naphthol-5-sulfo. 
I-NAPHTHALENE 5-Sulfo nitrated, reduced to amin and Na salts separated by solubility in aq. 
as in 333,034, then more soluble portion diazotized and boiled in dilute acid to form naphthol. 


348,4838—Aug. 31, 1886. Hugo von Percer, Austria-Hungary. 
Production of phenyl-methyl oxyquinicine. 


Hydrazo BENZENE, deriv. or homolog, is heated at g0-130° with 1-1.5 parts aceto ACETIC 
ether or deriv. for 4-5 hours, 


350,468—Oct. 5, 1886. Rudolf Scumitt and Carl Korgpe, Germany. (von Heyden.) 
Manufacture of naphthol-carboniec alkaline salts. Naphthol carbo acid, alkali 
salts. 


Dry alkali salts of 1 or 2-NAPHTHOL and dry CO, mixed at common temp. to form an addi- 
tion comp. (carbonic acid naphthol ether) which heated in autoclave at 1z0-140° is molecularly 
transformed. For first operation an autoclave and dry CO, gas or solid CO, may be used or 
pressure at 120-145°. 


351,056—Oct. 19, 1886. Fritz Krucer, Germany. 
Production of betanaphthol-disulpho acids. 2-Naphthol-3.6-disulfo salt, “R’” or 
a salt. 


2-NAPHTHOL is sulfonated to disulfo acids in 4 parts (66°) H,SO, that is first heated to 
125-135°, the naphthol added and temp. raised to 125-145° for 4-5 hours, the acid then one- 
half neutralized and resulting mixed sulfo acids separated by crystn. from brine. Insoluble di- 
sulfo acids of 2-naphthol when used as intermediates in azo dyes give redder shades than sol- 
uble sulfo acids. List of colors produced is given. 


352,361—Nov. 9, 1886. Oscar SCHRAUBE, Germany. (Badische.) 
Production of acetine-blue colors. Acetin. 


GLYCERIN is heated with 2 parts glac. acetic for 48 hours and excess acetic distilled off. A 
mixture of mono and di acetin with a small quantity of tri deriv. results. 


356,672—Jan. 25, 1887. H. VoiiBrecut and C. Menscuinc, New York. (Schoellkopf.) 
Red coloring matter from alpha diazo beta-naphthylamine sulphonic acid. 
1-Naphthylamin-5 or 8-sulfo, ‘S.” 
1-Sulfo NAPHTHALENE nitrated at 90-100° to form mixed alfa mono nitro compounds, re- 
duced and the (1.5) product separated from the (1.8) by the greater solubility of its Na salt in 
aq. The (1.5) acid is used for dye of same patent number. 


322 DIGEST OF PATENTS 


360,792—Apr. 5, 1887. F. Benner and G. Scuuutz, Germany. (Leonhardt.) 


Obtaining diazo colors by means of diamido-stilbene and diamido-fluorene. 
(Process.) Diamino stilbene and diamino fluorene. 


Two mols. of 4-nitro BENzyL chloride, or bromide, in alc. soln. are condensed by KOH to 
dinitro stilbene, then reduced by Sn and HCl, or 4-nitro toLuENE heated with alc. and NaOH, 
and red product reduced. Duiamino fluorene may be nitrated by HNO, and reduced. 


361,690—Apr. 26, 1887. Robert GnEHM, Switzerland. (Basle.) 


Production of a new ethyl-ether. (Product, not process, claimed.) Ethylene diamin 
diacetacetic ester, m.p. 126°. 


ETHYLENE diamin is heated in aq. with 3.3 parts aceto ACETIC ester. 


362,560—May 10, 1887. ' Arthur WEINBERG and Hans Sr1esErt, Germany. (Cassella.) 


Production of a new naphthylamine-monosulphonie acid. (Product, not process, 
claimed.) Naphthol sulfo and naphthylamin sulfo. 


I-NAPHTHALENE disulfo is heated to 200° with 50 per cent NaOH till acidified test gives 
trace of dioxy comp.,* dild., acidified, and boiled to drive off SO,. Heated with NH, in auto- 
clave to 250° product gives amin. 


362,592—May 10, 1887. Eduard Uuiricu, Germany. (Hdchst.) 
Trimethylethylthionin blue coloring matter. 4-Amino dimethyl anilin. 


Dimethyl aniLin in dil. HCl soln. is treated with HNO, then with Zn to reduce to amino 
comp. 


366,385 7—July 12, 1887. | Eduard Uniricu, Germany. (Hochst.) 


Blue ecoloring-matter formed from paranitroso-methyldiphenylamine on 
phenols or oxycarbonie acids. 4-Nitroso methyl diphenylamin. 


Methyl DIPHENYLAMIN is dissolved in 3.5 parts glac. acetic acid containing 0.63 part HCl, 
and 1 mol. nitrite added. 


369,764—Oct. 13, 1887. J. Munnueim, Switzerland. (Durand.) 
Manufacture of blue coloring-matter. Diphenyl naphthyl diamin. 


Dioxy NAPHTHALENE is condensed with 2 mols. ANILIN, or other primary amin, using CaCl,, 
ZnCl,, AlCl, and HCl, etc., or an amin chloride as condensing agent. 


374,259—Dec. 6, 1887. Adolph LirsmMann, England. 
Monosulpho-acid of alpha-naphthol. 1-Naphthol sulfo, which readily forms dinitro 
deriv. and couples with diazo comps. 
I-NAPHTHOL heated with 4 parts conc. H,5O, at 130°, barium salts formed and these, sus- 


pended in aq., saturated with gaseous HCl, refluxed, filtered and new acid separated from soln. 
as Ba salt. Other methods given. ‘ 


377,349—Jan. 31, 1888. Maurice CERESOLE, Germany. (Badische.)_ 


Production of new red coloring-matter. Dimethyl 3-amino phenol. m.p. 86°. 


3-Amino PHENOL, I part, with 3 parts METHYL alcohol is heated in closed digester at 170°, 
excess alcohol distilled off, neut. soda, extracted with ether and cryst. from ligroin, ete. 


377,350—Jan. 31, 1888. Maurice CrerEesoL.e, Germany, (Badische.) 
Production of new red coloring-matter. Diethyl 3-amino phenol, m.p. 74°. 


3-Amino PHENOL is heated in closed digester at 170° with etuyz alcohol, as in 377,349. 


380,067—Mar. 27, 1888. A. WEINBERG, Germany. (Cassella.) 
Production of new diamido compounds and of azo colors produced there- 
from. Ethoxy benzidin sulfo acid, or other. 
ANILIN azO 2.5-PHENOL sulfo with OH in ortho position to azo group, treated in alk.-alc. 
soln. with EtuHyL bromide or other halogen ester to form an ether which is less soluble in water 
than original comp., reduced by Sn and HCl, Zn dust or NaSH, etc., the metal removed by H,5 


* Ebert and Merz, Ber. IX, 612, failed to stop reaction at this point, so obtained dioxy 
naphthalene. 


> 


GROUP XXII.—INTERMEDIATES 323 


and the benzidin comp. pptd. by neutn. with alk. Heated in closed vesse! at 170° with water 
the sulfo acid of 2-ethoxy benzidin is formed. 


380,928—Apr. 10, 1888. A. F. Porrrter and Z. Roussin, France. (St. Denis.) 
Production of diazoic coloring-matters. 1-naphthylamin-6-or 7-sulfo acid. 


I-NAPHTHYLAMIN mixed with 3.5 parts fuming H,SO, (28-30 per cent SO,), below 25° and 
let stand 2-3 days, then converted to Na salt. Differs from Piria, Ewer or Pick’s acids. 


381,471—Apr. 17, 1888. FE. Hass—ENKAMP, Germany. (Dickerson.) 
Process of producing blue-red coloring-matter. Alkyl-1-naphthylamin-sulfo acid. 


I-NAPHTHYLAMIN sulfo acid, Na salt, in aq. soln. with 1 mol. mMretTuyt sulfate Na salt, heated 
to hours in an autoclave to 180—200°. 


382,832—May 15, 1888. Christian RupotpH, Germany. (Ocehler.) 
Production of yellow coloring-matter. (Product also claimed.) (a) Benzylidene 
3-toluylene diamin. (b) Tetra amino ditolyl phenyl methane. (c) Hydro diamino dimethyl 
phenyl acridin. : 
3-TOLUYLENE DIAMIN or other, mixed to paste with aq. and BENZALDEHYDE to form (a). 
Product heated in aq. to 60-70° with 3-toluylene diamin sulfate. Or in one operation benzalde- 
hyde heated with 3-toluylene diamin, NaOH and alc. (or 3-toluylene diamin HCl or sulfate and 
alc.) to form (b). Product (b) heated in autoclave at 160° with HCl to form (c). 


389,127—Sept. 4, 1888. Hans Wo .rFrf, Switzerland. 


Production of new azo colors. (Product also claimed.) 3-Nitro-4’.4”-diamino triphenyl- 
methane or homologs and derivs. 


3-Nitro BENZALDEHYDE, condensed with 2 mols. ANILIN, or other aromatic amin by refluxing 
4 hours with HCl (21°) to form 3-nitro 4’.4”-diamino triphenylmethane, etc. 


395,080—Dec. 25, 1888. Christian Rupo_pH, Germany. (Oehler.) 
Coloring-matter. Hydro triamino dimethyl phenyl acridin. 


Nitro tetra amino ditolyl phenyl METHANE HCl reduced in warm aq. soln. by SnCl, and HCl, 
diluted, Sn. pptd. by H,S and base pptd. from filt. by alkali, then product heated in auto- 
clave with HCl (16°). 


395,474—Jan. 1, 1880. F. Bayer, Germany. (Bayer.) 
Manufacture of dye-stuffs or coloring matters. 2-Naphthylamin 7-sulfo ‘Delta’ 
or F acid. 


2-NAPHTHYLAMIN sulfonated in 3 parts H,SO, at 150-170° for 1 hour, the alk. soln. pptd. 
at 80° with H,SO, and the new sulfo acid which remains in soln. crystd. on evapn. or pptd. as 
Ba or Na salt. 


396,574—Jan. 22, 1889. Alfred Kern, Switzerland. 
Formation of purple coloring-matter. (Product, not process, claimed.) Alkyl ester 
of dimethyl gallocyanin. 
Gauuic acid, or tannin, in 2.5 parts methyl alc. soln., treated with dry HCl vapor or with 
conc. H,SO,. 


403,678—May 21, 1889. Carl Kussmavut, Switzerland. (Basle.) 
Metaamidophenol. (Process, not product, claimed.) 3-Amino phenol, m.p. 121°. 

Caustic soda and a little aq. fused at 270°, to which aniLINn 3-sulfo is added and temp. 
kept at 280-290° for an hour, diluted, acidified, filtered to remove resins, neut. with alk. carb.; 
extracted with ether, purified, etc. : 


405,938—June 25, 1889. Momme AnpreEsen, Germany. (Berlin.) 


Manufacture of a new alpha naphthol-disulphoniec acid. (Product, not process, 
claimed.) 1-Naphthol-3.8-disulfo or 1-naphthylamin-3.8-disulfo. 


NAPHTHALENE disulfonated in H,SO, and cHLoRHypRIN or in fuming H,SO, (23 per cent 
anhyd) below 60°, nitrated, reduced, neut. by CaO, sodium salt formed, soln. conc., then cooled 
and filtered to remove (4.8-) comp. Soluble salt of patent (3.8-) is pptd. out of filtrate by acid. 
Corresponding naphthol results by diazotizing then boiling in dil. acid. 


324 DIGEST OF PATENTS 


407,906—July 30, 1880. Bruno R. Sr1Fert, Germany. (von Heyden.) 
Process of making paraoxybenzoie acid. 


PHENOL, as dry K salt, is heated in closed vessel under pressure at 180-250° and dry CO, 
forced in until salt is saturated. Pressure may vary from a little more than one up to 20 atms. 


410,295—Sept. 3, 1880. Rudolf Scumirt, Germany. (von Heyden.) 


Process of making beta-naphthol carbon acid. 2-Naphthol carbo acid, m.p. 216°, 
a stable form. 


2-NAPHTHOL, alkali salt, is heated with CO, under pressure to 200-250°. 
Note 350,468 for unstable acid by similar process. 


412,613—Oct. 8, 1880. Albert HEerrMANnN, Germany. (Hochst.) 
Coloring-matter. 3-Oxy tetra alkyl diamino triphenylmethane. 


3-Amino tetra ethyl diamino TRIPHENYLMETHANE, or other, with HCl and nitrite is heated 
to 60°, then boiled. Free base is pptd. by alkali. 


415,257—Nov. 10, 1880. Moritz Uxtricu, Germany. (Bayer.) 
Process of making dioxynaphthaline monosulpho-acid. Dioxy naphthalene sulfo 
acids. 


2-NAPHTHOL disulfo (R or G) is heated to 200° with strong caustic alkali, 


418,657—Dec. 31, 1889. Gustav ScHuLtz, Germany. 
Production of orange and red dye-stuffs. Diamino dimethyl stilbene sulfid. 


XYLIDIN, or other amino comp., 2 parts, is heated with 1 part sulfur as long as H,S escapes. 


420,373—Jan. 28, 1890. Otto N. Wirt, Germany. (Badische.) 
Ammonium salt of beta-naphthohydroquinone-beta-sulphonie acid. 1.2- 
Naphthohydroquinone sulfo, NH, salt. 


Amino 2-NAPHTHOL b-sulfo purified, is oxidized with HNO, to 1.2-NAPHTHOQUINONE sulfo, 
then purified by forming soluble sulfite comp. and pptd. by acids. Product is used in 420,372 
and 420,374 Group VI. 


423,550—Mar. 18, 1890. C. DuissErc, Germany. (Bayer.) 
Process of making blue dyes. Benzidin sulfone disulfo. 


Benzipin sulfate converted to sulfone by heating to 80° with fuming H,SO, (40 per cent 
anhyd.) is then heated at 160° until sol. in alk. and not pptd. by acetic acid (evidence of mono 
sulfo acid). 


425,525—Apr. 15, 1890. Jakob Scumip, Switzerland. (Basle.) 
Orthonitroparadiamido-diphenyl. 2-Nitro benzidin. 
BENnz1DIN sulfate dissolved in 10 parts (66°) H,SO, below 5° and HNO, added at this temp. 


427,564—May 13, 1890. Robert GNEHM and Jakob Scumip, Switzerland. (von Heyden.) 
Carboniec-acid compound of meta-amidophenol. 3-Amino phenol carboxylic. 

3-Amino PHENOL is heated with (NH,),CO,, or K or NaHCO,, and aq. in autoclave at 110°, 
soln. evaporated to small bulk, very slight excess of HCl added, impurities filtered off and carbo. 
acid pptd. by HCl. 


4.27,565—May 13, 1800. Robert GnEHM and Jakob Scumip, Switzerland. (Basle.) 
Carbonic-acid compound of dimethyl meta-amidophenol. Dimethyl 3-amino 
phenol carbo acid. 
Dimethyl 3-amino PHENOL, Na salt, heated in autoclave at 120-140° with compressed CO,. 


440,953—Nov. 18, 1890. W. Masgert, Germany. 
Blue dye. (Process and intermediate claimed, not dye.) 1.8-Dioxy naphthalene and mono 
or disulfo acids. 


NAPHTHALENE disulfonated by sulfuric acid cHLorHypRIN (C,H,.Cl1.0H.OSO,H), then fused 
in 3-4 parts NaOH, to form dioxy naphthalene (m.p. 248-252°), which may be mono sulfonated 


r 
| 
z 
: 


GROUP XXII.—INTERMEDIATES 325 


by conc. sulfuric at 60° or disulfonated by heating to 90-130°. Properties of this in compar- 
ison with other dioxy naphthalenes given in detail. 


444,679—Jan. 13, 1801. Moritz Utricu, Germany. (Bayer.) 
Dioxynaphthaline-mono-sulphonie acid. (Process also claimed.) 1.8-Dioxy naph- 
thalene-4-sulfo ‘“‘S.’’ 


I-NAPHTHOL 4.8-disulfo “S’’ heated in closed vessel at 240° with strong NaOH soln., etc. 
Open vessel may also be used. Azo dyes formed with derived diazo comps. are fast to light, 
air, and of bluer shades. 

Note 423,970 and 466,841 employ above acid Group VI. 


447,189—Feb. 24, 1891. Paul Junius, Germany. (Badische.) 
Red dye. Diamino diphenyl ketoxim. 

Diamino BENZOPHENONE (obtained by reduction of dinitro diphenylene ketone in hot alc. 
soln. with Na,S), in hot dil. HCl soln. to which HypRoxyLAmin HCl or other, is added; soln. 
then made alk., boiled and pptd. by acid as KETroxim. Product not very stable. 

Note intermediate is not claimed in patent. 


449,551—Mar. 31, 1891. Eugene Mentua, Germany. (Badische.) 
Dihydroxynaphthalene. 2.3-Dioxy naphthalene 6-sulfo ‘“R.’’ 

2-NAPHTHOL 3.6-disulfo “‘R’”? fused in NaOH at 240—280° until test portion neut. with HCl, 
filt. and soln. pptd. by NaCl gives highest yield of comp. 


449,551—Mar. 31, 1801. Eugene Mentua, Germany. (Badische.) 
Dihydroxynaphthalene.  2.3-Dioxy naphthalene. 


(a) 2.3-DIOXY NAPHTHALENE 6-sulfo is fused in NaOH at 300—320° until test portion, acid- 
ified, gives highest yield to ether, neutralized, filtered while hot, cooled and extracted with 
ether or fusel oil, etc. Product may be purified by crystn. from aq. (b) Or 2.3-dioxy naph- 
thalene 6-sulfo is heated in 25 per cent H,SO, in closed pressure resistant vessel to 200°. ‘Test 
for end of reaction is made by extracting with ether and coupling aq. ext. with diazo benzene 
in alk. soln. 


454,645—June 23, 1801. Leo Gans, Germany. (Cassella.) 
Amido-naphthol-monosulIphonie acid. 2-Amino 8-naphthol 6-sulfo, “Gamma.” 


” 


2-NAPHTHOL 6.8-disulfo, “Gamma,” of 331,059 treated with NH, to form 2-naphthylamin di- 
sulfo, which is heated in strong NaOH soln. in autoclave at 210°. Couples easily with diazo 
comps. in both acid and alk. soln. 

For derived dyes, see same number, and 442,369 Group VI. 


455,442—July 7, 18091. Jakob ScumMip, Switzerland. (Basle.) 
Betadelta-amidonaphthol. 2-Amino 7-naphthol. 

2-NAPHTHOL 7-sulfo heated with NaOH at 260—300°, is dissolved, partly neutralized, impur- 
ities filtered off, fully neut., filt. and amino naphthol separated from unchanged sulfo acid by 
soln. in dil. HCl. Special reactions for identification are given. 


456,081—July 14, 1801. Maurice CERESOLE, France. (Badische.) 
Red dye-stuff. Ethyl 3-amino phenol. 

Ertuyt chloride and METrANILIC acid are combined under pressure, then treated with alkali 
in usual way, or ethyl an1Li1Nn is heated at 60° in fuming sulf. acid (28 per cent SO,) then at 
same temp. or at 40° more fuming acid (75 per cent SO,) added. The dry sulfo acid, Na salt, 
is fused in KOH at 200-220° to form phenol. 


456,627—July 28, 1891.- C. A. Martius, Germany. (Berlin.) 
Process of making azo dyes.  1-Naphthol 4.8-disulfo “d’” or “S.” 


NAPHTHALENE disulfo obtained from NAPHTHALENE by treatment with fuming H,SO, or sul- 
furic monochlorhydrin, nitrated in alfa position, reduced and converted into naphthol. (Process 
not given.) 


456,897—July 28, 1891. C. A. Martius, Germany. 


Azo dye. (Process, not product, claimed.) 1-Naphthol 2.4-disulfo. 


NAPHTHALENE disulfo (from naphthalene and fuming sulfuric) nitrated, reduced, and con-. 
verted into naphthol deriv. 


326 DIGEST OF PATENTS 


458,284—Aug. 25, 1891. H. Kuzre.t, Germany. (Hochst.) 
Azo dye. Naphthol trisulfo acid monamid. 


NAPHTHALENE is trisulfonated, then nitrated and reduced to give NAPHTHYLAMIN trisulfo, 
which with nitrous acid and subsequent boiling with dil. acid yields a naphtho sultone disulfo 
acid which is converted by ammonia into naphthol trisulfo monamid. 


458,285—Aug. 25, 1801. Hans Kuze.t, Germany. (Hochst.) 


Amido-naphthol monosulphoniec acid. (Process also claimed.) 2-Amino 8-naphthol 
6-sulfo, diazotizable “R acid.” 
2-NAPHTHYLAMIN disulfo (from 2-naphthol disulfo and NH, or by sulfonation of 2-naph- 
thylamin) is heated in open or closed vessel with 2 parts NaOH and some aq. slowly to 260-280°. 
The sulfo groups are removed successively, the first stage yielding amino naphthol mono sulfo 
of patent. 


458,286—Aug. 25, 1891. Hans Kuzet, Germany. (Hochst.) 
Amido-oxynaphthaline disulphonic acid.  1-Amino-8-naphthol-3.6-disulfo. 

I-NAPHTHYLAMIN trisulfo obtained from NAPHTHALENE trisulfo by nitration and reduction, 
is heated with 2 parts NaOH containing % parts aq. to 220-260° till foaming ceases. Product 
may be combined in acetic or alk. soln. with diazo bodies. 


464,135—Dec. 1, 1891. M. Horrman, Germany. (Cassella.) 
Blue dye. (Process also claimed.) 1-Amino-8-naphthol-3.6-disulfo, ““H’’ acid. 


NAPHTHALENE 2.7-disulfo, dinitrated and reduced to diamino deriv. heated at 1oo—130° in 
dil. sulfuric acid, gives fine yellowish needles of acid ‘“‘H.”’ 


464,566—Dec. 8, 1891. M. Horrmann, Germany. (Cassella.) 
Blue dye. 1.5-Diamino naphthalene 3.7-disulfo. 


NAPHTHALENE 2.6-disulfo lime salt, dinitrated at common temp., is reduced with Fe and 
acetic acid. 


-471,659—Mar. 29, 1802. Eduard VoncERICHTEN, Germany. .(Héchst.) 
Process of making diamino-diphenylmethan bases. Diamino diphenylmethane 
bases. 
ANILIN is condensed with FORMALDEHYDE to form anhydro formaldehyde anilin which is 
heated at 100° with excess anilin and aninin HCl. Or DIPHENYLAMIN in alc. soln. at 60° is 
condensed with formaldehyde. Other components claimed. 


473,467—Apr. 26, 1892. Hans Kuzet, Germany. (Hoéchst.) 
Process of making naphthosultondisulphonic acid. (Product also claimed.) 
Naphtho sultone disulfo, for making chromotropic acid. 


NAPHTHALENE trisulfo, nitrated and reduced to NAPHTHYLAMIN trisulfo which is acted upon 
by sulfuric and nitrous acids in boiling aq. soln. till N ceases to evolve. Resulting sultone 
forms sulfamid with NH,, and with hot aq. or dil. alk. reforms the trisulfo acid and when heated 
strongly with alkali yields chromotropic acid. 


Note 511,892 Group VI. 


488,290—Dec. 20, 1892. Bruno R. Serrert, Germany. (von Heyden.) 
Process of making oxyuvitie acid. 

Cresot as dry alk. salt is heated to 160-220° in’ pressure vessel and CO, forced in to sat- 
uration. : 


493,562—Mar. 14, 1893. Jakob Scumip and Robert Pacanrini, Switzerland. (Basle.) 
Monosulpho-dioxynaphthoie acid. (Process also claimed.) Sulfo dioxy naphthoic 
acid. 


2-NAPHTHOL carbo heated in fuming H,SO, (24 per cent anhyd.) at 1oo-120° to form di- 
sulfo 2-NAPHTHOL carbo which is heated in conc. NaOH to 210-240° in’ closed or open vessel. 


Note 493,563 and 64 and 557,437. Group VI, which employ this intermediate. 


agi eg 


ea 


aa 


GROUP XXII.—INTERMEDIATES 327 


498,404—May 30, 1808. P, Ort, Germany. (Bayer.) 
Greenish-blue dye. (Process also claimed.) 4’-Tolyl 1-naphthylamin 8-sulfo. 


I-NAPHTHYLAMIN 8-sulfo 1 part, is heated with 4 parts 4-roLumpDIN and 1 part 4-toluidin HCl 
at 160-180° for 10 hours. Note anilin deriv. in 498,404, dye patent Group VI. 


498,882—June 6, 1893. © Meinhard HorrmMann, Germany. (Cassella.) 
Naphthylene-diamine disulpho-acid. (Process also claimed.) Naphthalene 1.5-di- 
amin 3.6-disulfo. 


NAPHTHALENE 3.6-disulfo nitrated below 10° to dinitro product, is reduced with Fe and 
acetic. Product can be tetrazotized and coupled with phenols, etc., to form valuable colors. 


511,532—Dec. 26, 1893. R. Korue, M. Uxricu, and O. Dresser, Germany. (Bayer.) 
Blue dye. (Process also claimed.) 1-Amino 8-naphthol 2.4-disulfo acid. 


1-Naphthylamin 4.8-disulfo acid, heated at 80-90° in 4 parts fuming H,SO, (40 per cent 
SO,) until a test gives no diazo deriv. or azo dye with a coupling agent; diluted, neut. with 
Ca(OH),, filt., and Na,CO, added to form Na salt then evap. and pptd. by alc. as yellow crysts. 
of the Na salt of naphthalene sodium imino sulfone disulfo acid. This is heated with 2.5 parts 
of potash or soda to 170°, and the amino naphthol disulfo acid pptd. from soln. as the acid Na 
salt by HCl. . 


511,708—Dec. 26, 1893. Max Moetuier, Germany. (Berlin.) 
Production of amido-naphthol disulfonie acid. (Product also claimed.) 1-Amino- 
8-naphthol-3.5-disulfo “Cleves”? (or 1.8.2.4). 
I-NAPHTHYLAMIN disulfo is trisulfonated in H,SO, (23 per cent anhyd.) and product fused 
in NaOH at 170-220° till fluorescence of alk. soln. disappears, and acid Na salt then formed. 


511,898—Jan. 2, 1894. Hans Kuze.t, Germany. (Hochst.) 
Naphthol trisulfonic-acid monamid. (Process also claimed.) Naphthol trisulfo mono- 
amid. 


I-NAPHTHOL 8-sultone 3.6-disulfo, Na salt, is mixed at ordinary temp. with 2-3 parts 20 per 
cent ag. ammonia. Ca or Mg salts of sulfo acid and alcoholic ammonia or ammonia gas can 
also be used. 

Addition to 473,467. 


516,585—Mar. 13, 1894. Heinrich A. BERNTHSEN, Germany. (Badische.) 
Red rhodamin dye. (Process also claimed.) Ethyl 3-amino-4-cresol. 


Ethyl 2-ro.uipin, or other, is heated in 2 parts fuming sulf. acid (23-70 per cent SO,) at 
60° to form para sulfo acid, the Na salt of product fused in NaOH at 220-260°, cooled, pptd. 
by acid and extracted by ether from sat. soda soln. 


516,752—Mar. 20, 1894. Johann J. Brack, Switzerland. (Durand.) 
Diamido base. (Process also claimed.) Asymmetric diamino bases suitable for production 

of substantive cotton dyes. 

ToLipIn, or other, and aniLin HCI condensed in alcohol with FORMALDEHYDE to form tolidin 
anilin methane, or other. 

Note 516,753, 54, 55, and 531,149. 


516,753—Mar. 20, 1894. Johann J. Bracx, Switzerland. (Durand.) 
Diamido base. (Process also claimed.) Asymmetric diamino bases for substantive cotton 
colors. 
To.pin, or other, and 3-PHENYLENE DIAMIN that has been half neutralized with HCl, are 


condensed in alcohol with FORMALDEHYDE. Other components claimed. 
Addition to 516,752. 


516,754—Mar. 20, 1894. Johann J. Brack, Switzerland. (Durand.) 
Diamido base. (Process also claimed.) as-Diamino bases for substantive colors. 
DIANISIDIN and basic 3-PHENYLENE DIAMIN (one-half neutralized with HCl) condensed in 
alc. soln. with FORMALDEHYDE. Other components claimed. 
Addition to 516,752. 


328 DIGEST OF PATENTS 


516,755—Mar. 20, 1894. Johann J. Brack, Switzerland. (Durand.) 
Diamido base. (Process also claimed.) as-Diamino bases, for substantive cotton colors. 


DIANIsIDIN and aniLIn HCl or 2-amino PHENOL are condensed in alc. soln. with FoRMAL- 
DEHYDE. 
Addition to 516,752. 


521,095—June 5, 1894. H. A. Berntusen and P. Junius, Germany. (Badische.) 


Substantive blue dye. 2-Amino 5-naphthol 7-sulfo. 
2-NAPHTHYLAMIN 5.7-disulfo is fused in caustic at 170-195°. 


Note Armstrong and Wynne, Proc. Chem. Soc., 1890, 128. 


524,069—Aug. 7, 1894. C. O. Miuier, Switzerland. (Basle.) 
Blue tetrazo dye. 1.7-Dioxy naphthalene 4-sulfo. 

t-Oxy 4.7-disulfo 2-NaPpHTHOIC acid is fused in NaOH at 230-—290°. 

Note 524,070. 


524,070—Aug. 7, 1894. C. O. Mi.uer, Switzerland. (Basle.) 
Blue tetrazo dye. (Process also claimed.) 1.7-Dioxy 4-sulfo 2-naphthoic acid. 

1-Oxy 4.7-disulfo 2-NAPHTHOIC acid is fused in NaOH, or other, at 180-200°. In 524,069 
the same material at a temp. of 230-290° yields dioxy NAPHTHALENE sulfo. 


§24,220—Aug. 7, 1894. C. Scurauset, Germany. (Badische.) 
Substantive blue dye. (Process also claimed.) Benzoyl 1-amino 8-naphthol 4-sulfo. 


I-NAPHTHYLAMIN 8-sulfo is fused in NaOH at 230-240° until all is sol. in dil. hot HCl, 
the resulting 1-AMINO 8-NAPHTHOL is sulfonated in conc. H,SO, below 20° till soluble clear in 
dil. NaOH, separated, dissolved in soda and BENzoyL chloride added, keeping temp. below 5°. 


524,221—Aug. 7, 1894. Conrad ScHrAuBE and Eugen Romic, Germany. (Badische.) 
Phenylrosindulin sulfo-acid. Phenyl rosindulin mono sulfo acid.* 

2-Amino 4-sulfo DIPHENYLAMIN and 2-OXY NAPHTHOQUINONE anil are boiled in diluted alc. 
(2:3) until dil. alk. soln. of separated ppt. is repptd. with excess alk. and mother liquor is not 
colored orange red on testing with naphthoquinone anil. Heated at 100° in 4 parts 96 per cent 
H,SO, the disulfo acids that are formed are violet-rED acid dyes. 


524,261—Aug. 7, 18094. C. L. Mtuuer, Germany. (Badische.) 


Orange diazo dye. 3-Phenylene diamin disulfo. 

3-PHENYLENE DIAMIN is mixed while cool with fuming H,SO, (40 per cent anhyd) then 
heated to 100-120°. At least 2 mols. of free SO, must be used, the amount of SO, above 2 
mols., however, may be varied inversely with the temperature. ; 

Note 524,262 gives same process Group VI. 


526,786—Oct. 2, 1894. Otto Manassrt, Germany. (Bayer.) 


Process of making phenol alcohol. 2- and 4-Oxy benzyl alcohol, homologs and derivs. 


PHENOL, or its di or trioxy, nitro, sulfo or carbo derivs. or alkyl esters, is condensed with 
FORMALDEHYDE by boiling in 10 per cent NaOH, or other caustic or carbonated alk. or cyanide. 


531,149—Dec. 18, 18094. J. J SBEAGK; Switzerland. (Durand.) 


Substantive red dye. (Process also claimed.) as-Di-, tri-, or tetra-amino bases for sub- 


stantive colors. 

To.iipIn is boiled in dil. HCl soln. with FoRMALDEHYDE till pptd. base is completely sol. in 
acid. Amount of material, strength of acid, quantity of solvent, temp. and time of heating in- 
fluence character of product. 

Addition to 516,752. 


532,125—Jan. 8, 1895. A. WEINBERG, Germany. (Cassella.) 
Blue disazo dye. (Process also claimed.) 1-Chlor 8-naphthol 3.6-disulfo. 


I-AMINO 8-NAPHTHOL 3.6-disulfo is diazotized, insol. diazo comp. filt. off and treated at 10° 


*Tsomer of 428,530 in that sulfo group is attached to benzene residue of naphth-phenazin 


nucleus Gr. V. 


i, il ee ili . 
NOR WAR ae 5h. 4 
a x 


GROUP XXII.—INTERMEDIATES 329 


with to per cent HCl and Cu,Cl, till all becomes soluble. Copper then pptd. by H,S and comp. 
in filt. pptd. by NaCl. 
Original patent for this compound is 464,135. 


532,479—Jan. 15, 1895. K. PatHE and O. Dresset, Germany. (Bayer.) 
Red dye. (Process also claimed.) 2-Amino 5-naphthol 1.7-disulfo. 

2-NAPHTHYLAMIN 5-Sulfo is further sulfonated at 100° in fuming sulf. acid (10 per cent 
$O,) to trisulfo comp. (2.5.1.7) then fused in KOH in closed vessel under pressure at 180° to 
form naphthol. 


533,463—Feb. 5, 1895. M. Horrmann, Germany. (Cassella.) 
Black azo dye. (Process also claimed.) Naphthalene 1.4-diamin 6- or 7-sulfo. 

I-NAPHTHYLAMIN 6 or 7-sulfo is acetylated, nitrated, reduced and saponified. The nitro 
naphthylamin sulfo comp. (1.4.6 or 1.4.7) formed as intermediate will dye wool in acid bath a 
yellow color, like Naphthol Yellow S. The finished product diazotizes and couples to form val- 
uable dyes. 


536,431—Mar. 26, 1895. M. Kaun and F. RunKxket, Germany. (Bayer.) 
Black dye. (Process also claimed.) 4.4’-Diamino diphenylamin 2’-sulfo. 

1-Chlor 4-NITROBENZENE 2-Sulfo and 4-PHENYLENE DIAMIN are heated together in dil. alk. 
soln. and resulting nitro amino diphenylamin sulfo reduced. 


536,524—Mar. 26, 1895. Wilhelm Herzsrerc, Germany. (Berlin.) 
Amidotriazin. (Process also claimed.) Amino triazins. 

Diamino azo BENZENE HCl (‘‘Chrysoidin’?) or other, and BENZALDEHYDE, etc., are heated 
in conc. HCl and acetic (1:4.5 parts) at 100°, diluted and pptd. by Na,CO,. Products are 
stable diazo comps. Sulfo acid may be formed by 3 to 6 parts fuming H,SO, (20 per cent 
anhyd.), at gentle heat for mono sulfo and at higher temp. for disulfo. 


536,878—Apr. 2, 1895. R. Kircuuorr, Germany. (Berlin.) | 
Black dye. 4-Phenylene diamin azo cresidin. 

Diazo 4-NITRANILIN is coupled with crestpin (CH,.OCH,.NH,-4.1.2) and product reduced by 
alk. sulfids. 


537,511—Apr. 16, 1895. Arthur WEINBERG, Germany. (Cassella.) 
Phenylamidonaphthosulfo acid. (Process also claimed.) Phenyl 2-amino 8-naphthol 
6-sulfo. 


2-AMINO 8-NAPHTHOL 6-sulfo ‘“‘Gamma’”’ and ANILIN HCl are dissolved in anilin and heated 
to 160°. Coupling test is made to determine end of reaction. 


538,183—Apr. 23, 1895. Jakob Scumip and Johannes Mouter, Switzerland. (Basle.) 
Blue dye. (Process also claimed.) 1.2-Naphthoquinone 7-oxy 4-sulfo. 


1-Nitroso 2.7-dioxy NAPHTHALENE is dissolved in cold bisulfite soln. to which conc. HCl is 
added to form 1-amino 2.7-dioxy NAPHTHALEND 4-sulfo, which is oxidized by HNO,. 


539,699—May 21, 1895. M. Moeuier, Germany. (Berlin.) 
Blue dye. (Process also claimed.) 1-amino 8-naphthol 2.4-disulfo. 

I-NAPHTHYLAMIN 2.4-disulfo is sulfonated to trisulfo (1.2.4.8) then fused in NaOH to form 
naphthol deriv. 


540,412-—June 4, 1895. Moritz Unricu and Johann BamMmann, Germany. (Bayer.) 
Amidonaphtholdisulfo acid. (Process also claimed.) 1-Amino 8-naphthol 3.6-disulfo 
“ey 7.2? 


I-NAPHTHYLAMIN 3.6.8-trisulfo obtained by nitration and reduction of NAPHTHALENE trisulfo, 
is fused with 2 parts NaOH at 180-190°, or higher temp., in open or closed vessels. 
Differences between acid of patent and of 458,285 are given in detail, For 1.8 dioxy acid, 


see 458,283. 


541,750—June 25, 1805. W. Herzperc and O. Weser, Germany. (Berlin.) 
Black dye. 1-Amino 8-naphthol 3.6-disulfo disazo dianilin. 

2-NITRANILIN, 2 mols. coupled in acid then alk. soln. with 1 mol. I-AMINO 8-NAPHTHOL 
3.6-disulfo is reduced with Na,S. 


330 DIGEST OF PATENTS 


541,859—July 2, 1895. Richard Korerr, Austria-Hungary. (Kinzlberger.) 
New amido base and colors therefrom. (Dyes not claimed.) Tetra amino ditolidino 
methane. 


2-TOLIDIN 2 mols., or other, in 66° H,SO, is condensed with 1 mol. 40 per cent FORMALDE- 
HYDE. Condensation product of 2-roLUIDIN is separated into two bases, § and L, by greater sol. 
of Na salt of latter in aq. and differs from product of Brack, 515,897 and 516,753, being a 
tetramino comp. united by two phenyl rests while Brack’s is diamino comp. united by two amino 
rests, etc. 

Note 543,712 for dye from above. 


§42,073—July 2, 1895. J. J. Bracx, Switzerland. (Durand.) 


Substantive cotton dye. (Process also claimed.) Probably two mols. dianisidin united 
by amino groups to form di-imino methane. 


DianisiDIN is boiled in dil. HCl soln. with FoRMALDEHYDE and base pptd. by ammonia. 


543,894—Aug. 6, 1895. Rudolf ReyHER, Germany. (Bayer.) 
Azin dye and process of making same. Phenyl 3-toluylenediamin. 


3-TOLUYLENE DIAMIN, or homologs, is heated in pressure vessel at 250-270° with 4 parts 
ANILIN, or homolog, and product purified and cryst. 
Note same process in 557,022 and 559,062 Group V. 


546,604—Sept. 17, 1805. Johannes Tu1ELE, Germany, (Badische.) 
Amido-tetrazotie acid and process of making: same, 


Amino GUANIDIN, 1 mol., is mixed with soln. of 1 equiv. of mineral acid, diazotized below 
40-45° and diazo salt recovered by crystn. Or to the soln. of diazo salt acetate or other weak 
alk., material is added in sufficient quantity to convert guanidin to acetate, and soln. evap. to 
dryness. 


554,974—Feb. 18, 1806. Heinrich Baum, Germany. 
Process of making orthohalogenphenol. 


PHENOL is heated at 150° in closed vessel and vapor of Br or other halogen forced in. The 
resulting ortho deriv. contains but small amount of impurities that may be removed by addition 
of caustic alk. Fused with NaOH or KOH product gives pyrocatechin. 


556,164—Mar. 10, 1806. C. Ris and C. Simon, Switzerland. (Geigy.) 
Gray dye and process of making same. Dialkyl 2-amino 8-naphthol 6-sulfo. 


2-NAPHTHOL 6.8-disulfo ‘‘G” is heated in autoclave with ALKYLAMIN to 250° and the result- 
ing dimethylated amino comp. fused in alkalies above 200°, or 2-AMINO 8-NAPHTHOL 6-sulfo is 
alkylated. 


563,382—July 7, 1806. Friedrich Krecxr and Ignaz RosEenserc, Germany. (Kalle.) 
Amidonaphtholdisulfo-acid “K.’? (Process also claimed.) 1-Amino 8-naphthol 4.6-di- 
sulfo “K.” 


NAPHTHALENE 1.5-disulfo stirred at 40° into sulfuric monohydrate containing o.2 parts of 
sulf. acid of 70 per cent anhyd., is heated to 80-90° to form trisulfo (1.3.5) then nitrated be- 
low 60°, reduced, separated as the acid and Na salt then fused in NaOH at 160-170°, Advan- 
tages of “K’’ over “H’’ acid given, and examples of azo dyes produced. : 


564,801—July 28, 1806. Traugott SANDMEYER, Switzerland. (Geigy.) 
Greenish-blue dye. (Process also claimed.) 2-Sulfo benzaldehyde. 


2-Chlor BENZALDEHYDE is heated in autoclave at 100—-200° with aq. sodium sulfite. 


572,723—Dec. 8, 1806. Christian RupotpuH, Germany. (Oehler.) 
Trisazo dye. (Process also claimed.) 3-Amino phenol 6-sulfo acid III or 5-amino 2-cresol 
3-sulfo acid III. ' 
ANILIN -3.4-disulfo, or 4-toluidin 3.5-disulfo, is fused with alkali. 
574,395—Jan. 5, 1807. 
Robert W. Cornetison, New Jersey, and William H. Warren, New York. 
Process of obtaining aceto derivatives of aromatic amins. Acetanilid and 
homologs. 


GROUP XXII,—INTERMEDIATES Bot 


An acetic acid salt, preferably K or Na, and a salt of the amin with HCl or H,SO, in 
equimolecular quantities or with slight excess of acetate, are refluxed at 125° or other appro- 
priate temp. 


574,396—Jan. 5, 1897. 
Robert W. CorneELison, New Jersey, and William H. Warren, New York. 


Process of obtaining aceto derivatives of aromatic amins. Acetanilid and 
homologs by less expensive process. 


Alkali acid salt of acetic acid with possibly a slight excess of acid is. heated at s50—-60° till 
dried, mixed with ANILIN or other amin, and refluxed at 100-125° for 12-24 hours. As acetan- 
ilid is formed the acetate returns to normal salt and absorbs excess moisture present. 


575,237—Jan. 12, 1897. - Benno Homo.ixa, Germany. (Hochst.) 


Process of manufacturing aromatic aldehydes. Benzaldehyde and 2- or 4-nitro 
benzaldehyde, etc. 


Benzyl aniL1n or homolog or nitro deriv. in 5-10 parts aq. is raised to boil by live steam 
and o.5 bichromate with mineral acid slowly added. Aldehyde is recovered by distillation. 


575,904—Jan. 26, 1807. J Christopher Ris, Switzerland. (Geigy.) 
Black azo dye. (Process also claimed.) 4.4’-Diamino ditolyl amin, or other. 


4-TOLUYLENE DIAMIN, HCI salt, or other, oxidized with 2-toLuip1n HCI in cold aq. soln. by 
bichromate to an indamin, then reduced by Zn and HCl. 


578,384—Mar. 9, 1807. Peter T. Austen and Herbert C. Tuttrr, New York. 
Process of making acetanilid, ete. Acetanilid mfr. using dilute acetic acid. 


ANILIN oil and 1.5 to 1.75 parts 50 per cent ACETIC acid are heated in autoclave at 150-160° 
and so lbs. pressure for 30 hours. Excess acid is preferable. 


578,839—Mar. 16, 1897. Bruno R. SErFERtT, Germany. (von Heyden.) 
Process of making aromatie nitrosulfo chlorids. 

NITROBENZENE mixed with 2 parts CHLORHYDRIN sulfuric acid is heated by indirect steam 
until all HCl has been evolved, diluted with ice and filt. and nitrobenene sulfo recovered from 
mother liquor by converting to Na salt, which by treatment with chlorides of mineral acids 
forms further small quantity of nitrobenzene sulfo chloride. 


587,75 7—Aug. 10, 1897. Ignaz RosENBERG and Friedrich Krecxrt, Germany. (Kalle.) 


Naphthylenediamin-sulfo-acid and process of making same. _1.3-Diamino 
mono-, di- or tri-sulfo naphthalene. 


1-NaruTuor 3-sulfo, 1-naphthol 3.6-disulfo, 2.8-dioxy naphthalene 6-sulfo, or the 1.3.6-tri- 
sulfo acid, etc., is heated in autoclave with alk. and ammonia to 160—190°. 
: Note 588,180 Group VI. 


593,347—Nov. 9, 1897. Fritz Benner, Germany. (Leonhardt.) 
Violet disazo dye. Ethyl 2-amino 5-naphthol 7-sulfo. 

Ethyl 2-NAPHTHYLAMIN HCl in conc. H,SO,, with fuming H,SO, (20 per cent SO,) at 40° 
gives two isomeric mono sulfo acids, one whose Na salt is soluble in alc., called ‘‘A,” and the 
other “B.”? More acid at 100-120° gives a disulfo acid which when heated with KOH at 200° 
produces above naphthol. Or 2-NAPHTHYLAMIN 5.7-disulfo is boiled with an1LIn to produce the 
phenyl deriv., then product fused at 210° in KOH. 


Note 521,095. 


595,787—Dec. 21, 1897. Adolf Scumipt, Germany. 
Purification of crude acetic acid. 
Apparatus is shown whereby the impurities in crude acetic acid may be oxidized by the 


counter current principle. The warmed acid is introduced at the top of a tall cylindrical closed 
vessel filled with nut sized coal or coke, is distributed over the filter and meets a rising current 


of oxygen under pressure. 
22 


232 DIGEST OF PATENTS 


595,897—Dec. 21, 1897. Henri R. Vina, France. 
Process of making paramidophenol. Paramino phenol by reduction process without 
loss of material. 


Oxy azo BENZENE or 2-nitro PHENOL or dinitro derivs., 2 parts, with 3 parts Na,S and 1 
part NaOH, is heated to 180°. Presence of caustic prevents formation of by-products and loss. 


596,043—Dec. 21, 1807. Carl von per Linpr, Germany. 
Process of distilling acetic acid. Pure colorless acetic acid, 65-85 per cent, free from 

sulfurous acid, acetone and empyreumatic products. 

Pyrolignite of lime is distilled with theoretical quantity of H,SO, in vacuum of not less than 
600 mm. at a temp. such as 26° which is below that at which the acid attacks tarry matters and 
below decomp. temp. of acetate and acetic acid. Less material is used, purer and more conc. 
acid produced, brown acetate can be employed with sulfuric acid, time is saved and output of 
plant increased. 


602,682—Apr. 19, 1808. Wilhelm Digrertt, Germany. (Hauff.) 
Process of producing orthotoluene sulfonie acid. 


Thio crEsoL is heated in alk. KMnO, (2.67 parts), until color disappears, then evap. to 
dryness. To oxidize still further and produce the benzene deriv. twice quantity of KMnO, is 
used and CH, removed by oxidation. 


606,437—June 28, 1808. Fritz Benner, Germany. (Leonhardt.) 
Amidonaphtholdisulfo-acid and process of making same. 1-Amifo 8-naphthol 
3.5-disulfo ‘‘B.” 
1-AMINO 8-NAPHTHOL 3-Sulfo is further sulfonated in conc. sulf. acid at common temp. 
Heated in 6 per cent NaOH at 230° the dioxy comp. is formed. 


606,470—June 28, 1808. Pierre P. Monnet, France. (Soc. Chim.) 
Process of making chlorin derivatives of tolaene. 2-Chlor benzylidin chloride, 
2-chlor benzal chloride and other chlorin derivatives of toluenes 


ToLUENE 2- or 4-sulfo chloride is heated to 150-200° while stream of dry Cl gas is passed. 
The para compound yields much of the trichlor deriv., and is purified by distillation at 155— 
165° under reduced pressure while the ortho comp. distils at 225-235° at ordinary pressure. A 
little PCl, aids chlorination. Product is used for making aromatic aldehydes, and acids. 


607,056—July 12, 1898. Joseph Koetscuet, France. (Soc. Chim.) 
Process of making aldehydo-benzoie acid. (Product also claimed.) 


Naphthalene or deriv., is oxidized by KMnO, to 2-oxalyl BEnzorc acid and the latter after 
separation is warmed at 80-100° with 3 mols. ANILIN and resulting diphenyl diammonium phenyl 
imid deriv. refluxed in 5 parts xylene or other neutral solvent. CO, is evolved. 


608,019—July 26, 1808. August BauscuiicHuer, Austria-Hungary. (Roessler-Hass.) 
Process of and apparatus for making acetone. 


Apparatus is shown in which dry acetate of lime (acrric acid, Ca salt) and 5 per cent 
Ca(OH), are treated with superheated steam, acetone vapors condensed and rectified under 


pressure. 


613,460—Nov. 1, 1898. Pierre P. Monnet, France. (Soc. Chim.) 
Process of making aromatic aldehydes. Aromatic aldehydes by direct oxidation of 
side chain. 


TOLUENE, homolog or deriv., and 2.5 parts 65 per cent H,SO, are mixed and 0.3 parts 
powd. MnO, slowly added *t about 40°, so that large excess CH, compound is always present. 


616,123—Dec. 20, 1808. Ivan Levinste1n and Carl MeEnscurnc, England. (Levinstein.) 
Process of making alphylamidonaphthol-sulfonie acids. Phenyl 1-amino 8-naph- 
thol 6-sulfo. 
1.8-Dioxy NAPHTHALENE 6-sulfo “G’” is heated to 160° with anitin HCl and ANILIN, or 
homolog. 


GROUP XXII.—INTERMEDIATES 333 


618,688—Jan. 31, 1890. Ernst Konic and Franz Scuoit, Germany. (Hdéchst.) 


Aromatic amidoammonium base and process of making same. 3-Amino pheny) 
trimethyl ammonium base that forms stable diazo comp. 


3-Nitro PHENYL trimethyl ammonium chloride is reduced by Zn and HCl or other to amino 
compound that is stable and may be diazotized and coupled with amins and phenols to form 
basic azo dyes. 


618,809—Jan. 31, 1809. Henry R. Vipat, France. 
Process of making amidophenols. 


SULFANILICc acid, or other aromatic amino sulfo acid, is mixed with 0.8 part MnO, to which 
3.5 parts 66° H,SO, is added and temp. raised to 60°. When reaction starts, outside heat is 
removed. After dissolving in aq. and removing Mn. the product crysts. from cooling soln. 


619,181—Feb. 7, 1809. Max H. Ister, Germany. (Badische.) 
Product from dinitro-naphthalene and process of making same. Dinitro 
naphthalene deriv. for mfr. of various types of brown, red or yellow dyes. 


1.8 Dinitro NAPHTHALENE or (1.5 deriv.) in 5 parts fuming sulf. acid (12-23 per cent 
anhyd.) is heated at 40-50° until sol. in NaOH with yellow color. Product can be converted 
by treatment with fuming (40 per cent $O,) H,SO, in presence of sulfur to a sol. brown 
YELLOW acid mordant (Cr) dye fast to light and milling. With sulfuric and boracic acids BROWN 
to RED dyes are obtained. On reduction a base that may be used for azo dyes results. 


620,368—Feb. 28, 1890. Jakob Scumip, Switzerland. (Basle.) 
Blue tetrazo dye and process of making same. 1.8-Naphthacetol 3.6-disulfo, or 
isomers. 


I-AMINO 8-NAPHTHOL 3.6-disulfo, heated to a boil in mixture of glac. acetic acid, acetic an- 
hyd., and anhyd. sod. acetate until no longer diazotizable. Diacet amino naphthol disulfo is 
formed as by-product but may be transformed into above by boiling in dil. acid or alk. 


622,854—Apr. 11, 1899. Benno HomoiKa and August Stock, Germany. (Hochst.) 
Nitrobenzyliden sulfonic acid and process of making same. 2- and 4-Nitro 
benzylidene anilin sulfo acids for production of nitro benzaldehyde, etc. 
2- or 4-Nitro benzyl aniL1In sulfo, Na salt, is oxidized in aq. soln. with KMnO,, or other, 
preferably in presence of CO, or MgSO,, while cooling and stirring. Products which exist only 
as salts decompose completely in aq. or dil. acid soln. to nitro benzaldehyde, etc. 


625,174—May 16, 1889. Ivan Levinste1In and Herman Preirrer, England. (Levinstein.) 
Substantive red tetrazo dye and process of making same. Dichlor diacet benz- 
idin. 


Diacet. BENzIDIN is dissolved in conc. sulf. to which sufficient Ca(OCl), is added to form 
dichlor benzidin, then saponified by boiling in dil. HCl. Or diacet. benzidin is suspended in 
salt soln., a little Fe wire added as carrier and chlorin gas passed in. 


625,637—May 23, 1890. Heinrich Berntusen, Germany. 
Oxynaphtindophenolthiosulfonice acid and process of making same. 


as-Dimethyl 4-PHENYLENE DIAMIN thio sulfo and 1-amino 2-naphthol 6-sulfo, in aq. soln. are 
made just neut. with NH,OH and at 12-15° a 24 per cent soln. of FeCl, is added. Nitroso 
naphthol or dioxy naphthalene derivs. may be used and other oxidizing agents. BLUE (Cr) to 
violet puuE (Al) acid mordant dyes fast to light and washing and adapted to printing. 


628,025—July 4, 1899. Carl OFHLSCHLAEGEL, Germany. (Berlin.) 
Blue-black wool-dye and process of making same. 4’-Amino 2’-sulfo phenyl 2- 
naphthylamin. 


4-Nitro chlor BENZENE 2-sulfo, heated for 12 hours at 160-170° in closed vessel with 1 mol. 
2-NAPHTHYLAMIN and a carbonate to absorb acid, reduced by HCl and Fe or Zn, etc., and pptd. 


as Na salt. 

628,5038—July 11, 1890. Ernst TwitcHELL, Ohio. 

Fatty aromatic sulfo compound and process of making same. Sulfo fatty aro- 
matic acids such as sulfo benzene stearic acid, C,H,(HSO,)C,,H,,0,, etc., stable catalyzers 
for hydrolysis of fats and oils. 


334 DIGEST OF PATENTS 


OxeErc acid or other fatty acid is mixed with 40 per cent of an aromatic comp. such as naph- 
thalene, bénzene, phenol, etc. and excess conc. H,SO, added below 30°. After standing, the 
conjugated sulfo comp. is freed from excess acid, naphthalene, or similar sulfo derivs. 


628,607—July 11, 1899. Bernhard Prigss and Oskar KaitwassEr, Germany. (Berlin.) 
Blaek dye. 4’-Oxy 2-nitro 4-sulfo diphenylamin. 


2-Nitro 1-chlor BENZENE 4-sulfo in aq. soln., is heated in closed vessel for two hours at 140°, 
with 1 mol. 4-amino PHENOL and a tarbonate. 


629,748—July 25, 1899. Ivan Levinsterin and Richard Herz, England. (Levinstein.) 


Blue-black disazo color and process of making same. Acetyl 1.4-naphthalene 
diamin 6- or 7-sulfo. 


ANILIN, coupled with 1-NAPHTHYLAMIN 6- or 7-sulfo, reduced as paste with Fe and acetic, 
is made alk., filt., and pptd. by slight excess acid, dried, powd., and acetylated by refluxing with 
65 per cent acetic acid and sod. acetate. Acetylation may take place before reduction of azo dye. 


631,606—Aug. 22, 1809. Oscar Batty, Germany. (Badische.) 


Halogen derivative of anthraquinone and process of making same. Halo- 
genated alphyl diamino anthraquinones. 


I.5-DINITRO ANTHRAQUINONE or crude dinitro anthraquinone, boiled in 10 parts ANILIN or 
other primary aromatic amin to alphyl amino product, is brominated (or Cl) in CS, or glac. 
acetic acid. Product condensed with an amin forms a dye that may be sulfonated. Table of 
reactions of various products is given. 


631,607—Aug. 22, 1899. . Oscar Batty, Germany. (Badische.) 
Dibrom anthraquinone derivative and process of making same. Dibrom 
1.5-diamino anthraquinone. 
Diamino ANTHRAQUINONE is suspended in 20 parts glac. acetic to which 2 parts Br are added 


at ordinary temps. A brick red powd., which crysts. from toluene in brown leaflets, diff. *sol. 
in alc. and glac. acetic, more readily in C,H,CH,, C,H, and C,H,NO, (YBr). 


631,608—Aug. 22, 18099. Oscar BatLy, Germany. (Badische.) 
Anthraquinone derivative and process of making same. _ Tribrom 1.5-diamino 
anthraquinone. 


1.5-Diamino ANTHRAQUINONE dissolved in 150 parts boiling glac. acetic acid, 2 parts Br added 
and soln. boiled until HBr ceases to evolve. A brown powd. or cryst. needles, diff. sol. cold 
alc., giac. acetic, CH, and C,H NO: 

Addition to 631,607, and note 632,621 for derived dye Group III. 


634,009—Oct. 3, 1890. Ivan LEvINSTEIN and Richard Herz, England. (Levinstein.) 
Blue-black tetrazo dye and process of making same. _ 1.4-Naphthalene diamin 
2-sulfo. 


ANILIN is coupled with 1-NAPHTHYLAMIN 2-sulfo, filt., dye reduced by Fe and HCl, soln. 
neut. by carbonate, anilin distilled off, and sulfo acid pptd. by HCl. 


636,043—Oct. 31, 1809. Benno Homo.ixa and August Stock, Germany. (Hochst.) 
Process of obtaining nitrobenzylanilin. 


2- or 4-Nitro TOLUENE chlorinated up to 50 per cent of w-chlor deriv. is mixed with equi- 
mols of ANILIN or homolog, and heated to 85-90°, when reaction starts temp. rises to 120-180° 
according to anilin base employed. Anilin HCl that forms as by-product is removed by boiling 
aq. and nitrotoluene in excess is distilled off. Other halogens may be used and part of anilin 
be replaced by alk. or alk. earth salt or NH. 

Note 636,994. 


636,994—Nov. 14, 1899. Benno Homo.ika and August.Stock, Germany. (Hochst.) 
Process of obtaining ortho and para nitro benzaldehyde. 


4-Nitro BENZYLIDENE sulfo, or ortho comp., Na salt, made as described in 636,043, is neut. 
in aq. soln. by HCl and the free acid thus liberated decomposes at once into 4-nitro benzalde- 
hyde which ppts., leaving anilin sulfo acid or homolog in soln. Or to original benzylidene comp. 
is added a soln. of 1 mol. anilin or other primary amin and separated 4-nitro benzylidene-anilin 
is boiled in dil. mineral acid. 


GROUP: XXII.—INTERMEDIATES 335 


637,183—Nov. 14, 1899. Henry Trrrisse and Georges Darier, Switzerland. (Badische.) 
Yellow basic dye. 2.4-Diamino 5-methyl toluyl alcohol. 


3-TOLUYLENE DIAMIN mixed in aq. soln. with FORMALDEHYDE at usual temp. 


640,564—Jan. 2, 1900. Benno Homoika and August Stocx, Germany. (Héchst.) 
Process of making amidobenzaldehyd. 

2-Amino BENZYLIDENE anilin sulfo acid or homolog is distilled with steam. Resulting 2-amino 
BENZALDEHYDE is carried over while anilin sulfo remains in soln. The corresponding para benz- 
ylidene comp. preferably is treated with bisulfite and aldehyde retained in soln. while anilin is 
distilled over because para comp. is not volatile with steam. 


640,989—Jan. 9, 1900. M. Bonicer, Switzerland. (Sandoz.) 
Blueish-red azo dye. Alphyl 1-sulfamino 8-naphthol 3.6-disulfo or other. 

I-AMINO 8-NAPHTHOL 3.6-disulfo or other dissolved at 70° in aq. containing chalk and to this 
mixture is added 4-roLvENE sulfo chloride, or other, temp. raised to 80° until diazo test reaction 
fails, then boiled and NaOH added to split off alphyl sulfamino radical from hydroxyl group. 
The alphyl sulfamino group attached to NH, group is unchanged. Soln. is neut. with HCl and 
pptd. by Na,CO,, etc. 


641,100—Jan. 9, 1900. Hermann Gussmann, Germany. (Hochst.) 
Process of making para-oxy-para-amido-ortho-oxydiphenylamin.  2.4’-Dioxy 
4-amino diphenylamin. 


4-Nitro chlor BENZENE 2-sulfo, is heated in sod. acetate soln. in closed vessel at 120° with 
4-amino PHENOL to form 4’-oxy 4-nitro DIPHENYLAMIN 2-sulfo, which is reduced, then heated in 
strong alkali at 150-200° and pptd. by acid. Gray white needles, sol. in hot aq. 


644,235—Feb. 27, 1900. P. Juuius, Germany. (Badische.) 
Black disazo dye. 2-Nitro 4-amino phenol 6-sulfo. 


4-Amino PHENOL 6-sulfo is dissolved in 95 per cent sulfuric, cooled to 5°, and mixture of 
HNO, and sulfuric monohydrate added below 0°. 


644,236—Feb. 27, 1900. P. Juuius, Germany. (Badische.) 
Black disazo dye. 4-Nitro 2-amino phenol 6-sulfo. 
2.4-Dinitro PHENOL 6-sulfo in dil. KOH soln. is reduced by Na,S below 20°. 


644,239—Feb. 27, 1900. P. Jutius, Germany. (Badische.) 
Black disazo dye. 2-Chlor 6-amino phenol 4-sulfo. 


2-Nitro 6-amino PHENOL 4-sulfo is diazotized and diazo comp. chlorinated in HCI soln. with 
“molecular” copper (Gatterman), then reduced by Fe and acetic. 


644,331—Feb. 27, 1900. Eugen Sapper, Germany. (Badische.) 
Process of making phthalic acid. 

NAPHTHALENE, I part in 15 parts sulfuric (100 per cent) and o.5 pts. HgSO,, is warmed 
until dissolved, then heated in retort gradually to 200° (reaction begins) then more rapidly to 
250° (SO, and CO, evolved) then to 300° or higher until solid or viscous. . Distillate consists 
of dil. sulf. acid and phthalic anhyd. with some sulfo phthalic. Filter or centrifuge. Other 
original materials derived from naphthalene nucleus are claimed and proportions of ingredients 
given. 


647,237—Apr. 10, 1900. F. Scumipt, Germany. (Hochst.) 
Diamidodiphenylamin sulfonic acid and process of making same. = 4.4’/-Di- 
amino diphenylamin 2.2/-disulfo (or 4.4’.2.3’ deriv.) 
4-PHENYLENE DIAMIN 2-sulfo is refluxed with 4-nitro chlor BENZENE 2-sulfo in dil. alk. carb. 
soln., pptd. by acid and reduced with Fe and acetic, filt. and re-pptd. by acid. 


648,261—Apr. 24, 1900. Benno Homo.ixka and August Stock, Germany. (Hoéchst.) 
Nitrobenzylanilin sulfonic acid and process of making same. 

2- or 4-Nitro BENzyL chloride and aniLin sulfo or homolog in dil. Na,CO, soln. are heated 
at 60-100°. Or a mixture of nitro benzyl chloride with nitro toluene obtained by partial chlor- 
ination of the latter may serve as first component. Other alkaline reagents may be used. 


330 DIGEST OF PATENTS 


648,389—May 1, 1900. Harry O. Cuurts, Canada, 
Process of making acetone. 

Apparatus is shown and described whereby acetates or other salt of fatty acid, in finely 
divided state or in thin layers or films are subjected to the exact temp. to liberate ACETONE or 
other ketone which is simultaneously removed from hot alk. mass to prevent decomp. A cir- 
culating pump keeps reaction chamber free of acetone, a vacuum being maintained or steam or 
any oxygen free gas passed through. 


648,753—May 1, 1900. Paul Jutius, Germany. (Badische.) 
Blue-black sulfur dye. 4’.4”-Dioxy 3'.3”-dicarboxy diphenyl 4.6-dinitro 1.3-phenylene di- 
amine. 


4.6-Dinitro 1.3-dichlor BENZENE, 1 mol., is refluxed in aq. soln. with 2 mols. amino SALICYLIC 
acid and enough sod. acetate to bind liberated mineral acid. 


648,754—May 1, 1900. Paul Jutius, Germany. (Badische.) 
Green-black sulfur dye.  4/.4”-Dioxy 3’.3”-disulfo diphenyl 4.6-dinitro 1.3-phenylene 
diamin. 


4.6-Dinitro 1.3-dichlor BENZENE, is refluxed in aq. soln. with 2 mols. 4-amino PHENOL 2-sulfo 
and sufficient sod. acetate to bind mineral acid. 


648,755—May 1, 1900. Paul Jutius, Germany. (Badische.) 
Black sulfur dye. 4'.4”-Dioxy diphenyl 4.6-dinitro 1.3-phenylene diamin. 

4.6-Dinitro 1.3-dichlor BENZENE, is refluxed in alc. soln. with 2 mols. 4-amino PHENOL HCl 
and sufficient sod. acetate to bind mineral acid. 


649,714—May 15, 1900. Johann BAMMANN and Walter Vorster, New York. (Elberfeld.) 
Dinaphthylamin sulfo derivative and process of making same. _ 5.5’-Dioxy 
2-dinaphthylamin 7.7’-disulfo. 
2-AMINO 5-NAPHTHOL 7-Sulfo, is heated to 80-100° in strong alk. soln. with bisulfite, 2 mols. 


condensing to dinaphthyl comp. 
Note 656,620 and 21 employ above as intermediate Group VI. 


650,327—May .22, 1900. Paul Junius and Friedrich Revsoip, Germany. (Badische.) 
Black sulfur dye. 2.4-Dinitro 5-amino 4’-oxy diphenylamin. 

4.6-Dinitro 1.3-dichlor BENZENE, is refluxed in alk. soln. containing sod. acetate with 1 mol. 
4-amino PHENOL, and the isolated 2.4-Ginitro 5-chlor 4’-oxy DIPHENYLAMIN heated in alc. NH, 
at 150—-160°. ‘ 


650,332—May 22, 1900. Max Manpt and Robert HotpMann, Germany. (Badische.) 
Process of oxidizing orthonitrotoluene. 2-Nitro benzaldehyde or 2-nitro benzoic acid 
made by regulating conditions of same process. 
2-Nitro TOLUENE in 10 parts 35-48 per cent H,SO, is mixed with 2 parts MnO, and heated 
4n pressure vessel at 140-165° for 2-3 hours at not more than 10 atms. to produce 2-nitro benz- 
aldehyde. For the benzoic acid deriv. stronger acid (62-78 per cent) and temp. of only 135- 
145° should be used, and pressure vessel is not necessary. <A reflux condenser will suffice. 


651,061—June 5, 1900. Arthur WEINBERG, Germany. 
Diamidonaphthol, 1.7-Diamino 2-naphthol. 


2-AMINO 7-NAPHTHOL in HCI soln. is pptd. in finely divided condition by excess Na,CO, and 
diazo ANILIN added. Separated dye is reduced by Fe filings in HCI soln. and diamino naphthol 
salted out. Or original amino naphthol is diazotized and soln. made alk. with Na,CO, The 
intra molecular azo comp. ppts. out and is reduced by adding gradually to SnCl, soln. 


653,678—July 17, 1900. Adolf Israrti and Richard Kotur, Germany. (Elberfeld.) 
Thio-urea compound and process of making same. _5.5’-Dioxy 7.7’-disulfo 2.27-di- 
naphthyl thio urea. 
2-AMINO 5-NAPHTHOL 7-Sulfo, 2 mols., is refluxed in neut. or alk. 50 per cent alc. with CS, 
and S. Product will combine with 1 or 2 mols. diazo comp. to form azo dyes. ‘ 
» Note 675,630. 


GROUP XXII.—INTERMEDIATES Ses 


655,117—July 31, 1900. Fritz Rascuic, Germany. 
Process of separating meta and para cresol. 
Commercial crEson is heated with conc. or fuming H,SO,, and the 4-cresol sulfo acid cryst. 


as hydrate from mother liquor by addition of small amount aq. By splitting off sulfo group by 
means of superheated steam the cresols can be obtained in pure state. 


655,529—Aug. 7, 1900. Joseph TurNER, England. 
Amidosulfonie acid. Amino sulfo salicylic acid, or other. 
2 or 4-Nitro sanicyLic acid, or similar derivs. of phenol, benzoic acid, etc., is boiled with 


10 parts bisulfite until yellow color of nitro comp. has disappeared, then soln. boiled with excess 
HCl to remove SO,,. 


656,120—Aug. 14, 1900.  , JuLius, Germany. (Badische.) 
Yellow azo dye and process of making same. Nitro 3-phenylene diamin sulfo. 


3-Dichlor BENZENE sulfo is nitrated in mixture of nitric and sulf. acids free from aq. to 
form nitro dichlor BENZENE sulfo which is heated at 130-160° with NH,. 


656,263—Aug. 21, 1900. Fritz Rascuic, Germany. 
Process of separating cresols. 


Com’l crRESOL (60 per cent meta, 40 per cent para) is sulfonated in 4-3 parts conc. or fuming 
acid (20 per cent SO,) at 100° or usual temp. respectively, and superheated steam of 120-130° 
applied after diluting acid to a strength that boils at 125-130°. Meta cresol distils over and 
para cresol at this temp. remains in soln. as the sulfo acid. At a temp. of 140-160° para cresoi 
may be distilled. | 


656,646—Aug. 28, 1900. Adolf Israky and Richard Koruzr, New York. (Elberfeld.) 
Urea derivative of amidonaphthol sulfonic acid and method of pt LES 
same, 5.5’-Dioxy 7.7’-disulfo 2-dinaphthyl urea. 
PHOSGENE vapors are passed into an alk. aq. sol. of 2-AMINO 5-NAPHTHOL 7-sulfo at usual 


temp. One mol. of phosgene combines with 2 mols. sulfo deriv., HCl being eliminated. 
Note 675,627. 


659,496—Oct. 9, 1900. Richard TaccEsett, New York. (Schoellkopf.) 
Meta-amidotolyloxaminsulfo-acid. ‘m-Amino tolyl oxamin sulfo acid A” or oxalyl 

3-toluylene diamin 6-sulfo. 

3-TOLUYLENE DIAMIN 6-sulfo is heated in aq. soln. with 2 parts oxaLic acid at 9go0—100° 
for 24 hours. Purified as Ca salt, diazotized and combined with ‘“R salt” product forms 
orange-red acid azo dyes. 

Note 659,497. 


659,497—Oct. 9, 1900. Richard Taccrsett, New York. (Schoellkopf.) 
Meta-amidotolyloxaminsulfo-acid. ‘m-Amino tolyl oxamin sulfo B” or oxalyl (2)* 

3-toluylene diamin 5-sulfo. 

(2)*3-TOLUYLENE DIAMIN 5-sulfo is heated in 3 parts oxaLic acid at 90-100° for 24 hours. 
Product combines with “R salt”, or other to form orange acid azo dyes. 

Note 659,496. *Denotes position of CH,. 


661,821—Nov. 13, 1900. Paul SripeL and Ludwig Preuss, Germany. (Badische.) 
Process of making anthranilic acid. 


2-Nitro TOLUENE and nearly equal parts NaOH in alc. soln. are refluxed until odor of nitro 
comp. has disappeared, the mixture saturated with NH, and H,S and boiled several hours. 
Anthranilic acid is finally pptd. from soln. by CuSO, Or 35 per cent aq. NaOH is heated to 
100° and equal parts 2-nitro toluene gradually added at this temp. 


661,872—Nov. 13, 1900. Henry S. A. Hout, Germany. (Badische.) 


Process of making nitrobenzaldehyde. 


2-Nitro TOLUENE is boiled with 0.6 parts finely powd. MnO, (80 per cent pure) for 1-2 hours 
and aldehyde separated as bisulfite comp. Or vapors of 2-nitro toluene are passed through a 
tube containing MnO, at 210-250°. Para nitro benzaldehyde can be prepared in similar way. 


338 DIGEST OF PATENTS 


664,709—Dec. 25, 1900. Alfred AMMELBURG, Germany. (Hiéchst.) 
Process of rendering nitroso bases stable. 


Nitroso DIMETHYL ANILIN HCl, purified, is mixed with a little aq. and Na,CO, or other salt 
of weak alk. reaction, such as acetate, phosphate etc., to combine with HCl. 


666,579—Jan. 22, 1901. J. J. A. Triwwat, France. (Soc. Chim.) 
Method of producing vapors of formaldehyde. Setting formaldehyde free from its 
solutions. 


To a soln. containing FORMALDEHYDE a neutral soluble substance is added, thereby tratsing 
the b.p. above the normal b.p. for formaldehyde, and soin. is then heated under pressure so 
that dry formaldehyde vapors are volatilized. 


666,866—Jan. 29, 1901. J. Herpasny, Germany. (Oehler.) 

Blue cotton dye and process of making same. Diazo 2-amino 8-naphthol 6-sulfo, 
sulfurous acid salt. 

. 2-AMINO 8-NAPHTHOL 6-sulfo diazotized, separated and ground, is mixed with sod. acetate 

and poured at o° into dil. NaHSO,, stirred till diazo body disappears, then neut. with soda. 

Soln. may be directly used for preparing dyes. 


667,358—Feb. 5, 1901. Johann Brurens, Germany. 
Process of manufacturing acetic acid. 

One part dry acetate of lime (82 per cent) is added to 1 part acetic acid of at least 60 
per cent strength and the theoretically sufficient quantity of H,SO, slowly added (0.55 parts of 
92 per cent acid). Artificial heat is not required. Acetic acid can be distilled, expressed or 
removed by suction. § 


667,382—Feb. 5, 1901. Lorenz Acu, Germany. (Boehringer.) 
Aromatic amido-aldehyde and process of making same. Dimethyl 4-amino benz- 
aldehyde, or other. 

Dimethyl aniLin or cther, and ALLOXAN are combined as described by Pellizari (Gaz. Chim. 
Ital., 17, 412) and product heated to 155° in 5 parts H,SO, (1.8). Gases are evolved and when 
this ceases soln. is diluted and neut. to ppt product. Similar processes can be used to produce 
a large number of aldehydes. Extraction of neut. soln. with ether is necessary in some cases. 


668,580—Feb. 19, 1901. Ivan Levinste1In and Richard Herz, England. (Levinstein.) 
Bluish triphenyl methane dye and process of making same. 4-Nitro 2-sulfo 
benzaldehyde. 


4-Nitro TOLUENE 2-sulfo is warmed in aq. to 70-75° and alk. soln. of NaOCl gradually 
added. When the liquid no longer evolves Cl with acid, it is neut. with mineral acids. 


670,398—Mar. 19, 1901. J. Hersasny, Germany. (Ocehler.) 
Blue triazol dye and process of making same. 4’-Sulfo phenyl 3.6-dioxy 1.2-naph- 
thyltriazole. 


SULFANILIC acid azo 2-naphthylamin 3.6-disulfo is converted into phenyl naphthyl triazole 
trisulfo, then heated :n 60 per cent NaOH at 230°. 


675,434—June 4, 1901. Emil Zacuarias and Eugen Brernuarp, Germany. (Griesheim.) 
Process of making nitronaphthalene derivatives. 1.4-Nitronaphthol or 1.4-nitro- 
naphthylamin, ethers and alkyl derivs. : 


1-Nitro 4-chlor NAPHTHOL is heated under pressure with aq. solns. of caustic alks., acid or 
neut. alk. carbonates or acetates, with alcohol present. The corresponding naphthylamin derivs. 


result when NH, is used. 


675,627—June 4, 1901. Adolf IsrazL and Richard Korur, New York.  (Elberfeld.) 


Urea derivative and process of making same. _ 5.8’-Dioxy 7.6’-disulfo 2-dinaphthyl 
urea, 


PHOSGENE and 1 mol. each of 2-AMINO 5-NAPHTHOL, 7-sulfo and 2-AMINO 8-NAPHTHOL 6-sulfo 
are condensed in aq. carb. soln. to form urea. » 
Addition to 656,646. 


E 
* 


GROUP XXII.—INTERMEDIATES 339 


675,628—June 4, 1901. Adolf Israry and Richard Korue, Germany. (Elberfeld.) 
Thio-urea compound and process of making same. Similar product to 653,678 
with OH and SO.H in one naphthol nucleus in 8.6 instead of 5.7 positions. 
2-AMINO 5-NAPHTHOL 7-Sulfo and equal parts 2-AMINO 8-NAPHTHOL 7-sulfo are mixed in 


large vol. 50 per cent alc. which is made slightly alk. with Na,CO, and refluxed with 2 parts 
CS, and a little S until H,S ceases to evolve, distilled to remove alc. and sulfur filt. out. 


675,630—June 4, 1901. Adolf IsraEL and Richard Korus, Germany. (Elberfeld.) 
Urea compound and process of making same. _5.5’-Dioxy 7.7’-disulfo 1.2’-dinaphthol 
urea. 


2-AMINO 5-NAPHTHOL 7-sulfo and 1-AMINO 5-NAPHTHOL 7-sulfo are condensed with PHOSGENE 
by passing vapors of the latter into a dil. Na,CO, soln. of equal parts of the former. 
Note 653,678. 


675,631—June 4, 1901. Adolf IsrarL and Richard Kotusr, Germany. (Elberfeld.) 


Thio-urea compound and process of making same. 5.5'-Dioxy 7.7’-disulfo 1.2/-di- 
naphthol thio urea. 


Process similar to 675,630, employing CS, and S in so per cent alc. soln. for condensation. 


676,860—June 25, 1901. Fritz Acu, Germany. (Boehringer.) 
Paraamidophenyl-glyoxylic acid and process of making same. 

ANILIN alloxan is dissolved in 2 parts boiling ro normal KOH. After evolution of NH, 
ceases soln. is evap. with stirring and di-potassium salt of 4-amino phenyl TarTrRoNIc acid re- 
covered as fine needles which may be dissolved in alk. and re-pptd by acid. When oxidized 
with MnO, in boiling aq. CO, is evolved and amino phenyl glyoxyllic acid results. Homologs 
and derivs. claimed and process given in detail. 

Note 667,382. 


677,514—July 25. 100.1. Adolf Israr, and Richard Kotur, New York. (Elberfeld.) 
Guanidin compound and process of making same. _5.5/-Dioxy 7.7/-disulfo 2-di- 

naphthyl guanidin. 

2-AMINO 5-NAPHTHOL 7-Sulfo, 2 mols. (not ortho or peri compounds) is condensed with CS,, 
S and alc. to form 5.5’-dioxy 7.7’-disulfo dinaphthyl thio urea, which is heated with NH, and 
PbO, to form guanidin deriv. Primary amins may be used for NH,. 

For derived dyes, see 677,516 and 17. 


677,515—July 2, ro9or. Adolf Israzt, and Richard Kotusr, New York. (Elberfeld.) 
Mixed guanidin derivatives and process of making same. _ 5.8’-Dioxy 7.6/-di- 
sulfo 2-dinaphthyl guanidin, 
Same as 677,514 except 2-AMINO 8-NAPHTHOL 6-sulfo is substituted for one of the (2.5.7) 


derivs. 
For derived dyes see 677,516 and 17 Group VI. 


679,199—Mar. 1, 1902. Julius AseL, Germany. (Badische.) 
Blue sulfur dye and process of making same. Dimethyl amino indophenol thio 


sulfo, or other. 


Dimethyl 4-PHENYLENE DIAMIN thio sulfo and PHENOL are condensed by oxidation with 
bichromate in acetic acid soln. 


682,510—Sept. 10, 1901. Walter VoIGTLANDER-TETZNER, Germany. (Badische.) 
Blue disazo dye. Phenyl 2-amino 5-naphthol 7-sulfo, or ‘‘Phenyl I-acid.* 

2.5-Dioxy NAPHTHALENE 7-sulfo, is heated together with ANILIN in 4o per cent (NH,),SO,, 
made alk. with Na,CO,, anilin distilled off, made acid, and cooled to ppt. sulfo acid. 
683,120—Sept. 24, 1901. Oskar KaLtwassER and Hugo Jarsscu1n, Germany. (Berlin.) 
Black disazo dye. 4-Chlor 2-amino phenol 6-sulfo. 


4-Chlor 2-nitro PHENOL reduced and sulfonated by refluxing with bisulfite, boiled with excess 
HCl to remove SO,. 


* Not claimed in patent. 


340 DIGEST OF PATENTS 


683,464—Oct. 1, 10901. Bernhard Heymann, Germany. (Elberfeld.) 
Process of making acetic anhydrid. 

Chlorine, 2 mols., and a little more than 1 mol. SO, are jointly introduced into a closed 
vessel containing 4 mols. dry sodium acetate, cooling to 20°. SO, must alwayg be present in 
slight excess. Gases are immediately absorbed and acetic anhyd. is distilled off in vacuum. 


685,895—Nov. 5, 1891. Ernst WirtH, Germany. 
Process of purifying anthracene. Purifying anthracene and recovering purifying agent. 
Crude ANTHRACENE is suspended in an indifferent liquid such as light oils, petroleum ben- 
zine, CS,, CCl, etc., or heated until it dissolves, then is treated with HNO,, either as gas or 
as nitrite in acid soln. Nitroso comps. of CARBAZOLE and homologs readily form and dissolve 
and are separated by filtration from purified anthracene after cooling. Soln. also contains 
PHENANTHRENE. Methods of prepn. of carbazole derivs. and applications are given. 


687,171—Nov. 19, 1901. Moritz Utricu and Karl HerrpEnricu, Germany. (Elberfeld.) 
Disazo dye and process of making same. 4.4’-Diamino 3.3/-disulfo diphenyl urea. 

PHOSGENE is condensed with 4-NITRANILIN 3-sulfo and produet reduced, or is condensed 
directly with 4-PHENYLENE DIAMIN 3-sulfo. 


690,325—Dec. 31, 1901. Paul SemeEL, Germany. (Badische.) 
Acid salt of phenyl-glycocol-ortho-earboxylic acid and process of making 

same. Improved yield of phenyl glycocol 2-carbo acid. 

ANTHRANILIC acid in paste is carefully neutralized with NaOH (35 per cent) and soln. of 
1 mol. chloracetic acid added to this neutral salt at low temp. then kept at 40° for several days, 
resulting in the acid salt or C,H,NH.CH,.COOH.COONa. The diacetate is not formed and 
at temp. employed the escaping HCl cam do no harm. Product is diff. sol. in aq. (1.5 per cent 
at 23°) and forms colorless crysts. when cooled. 


690,724—Jan. 7, 1902. Josef I. HawniczEx, England. 
Process of making acetone. 

Apparatus is shown wherein wood or other suitable carbonaceous material previously im- 
pregnated, coated or mixed with the oxide, hydrated oxide or carbonate of an alk. earth or with 
similar comps. of certain heavy metals, is subjected to destructive distillation, in closed vessel be- 
low bright red heat, and vapors condensed and recitified. 


691,132—Jan. 14, 1902. Hugo GERRESHEIM, Germany. 
Process of reducing nitro compounds. Nitro comp. reduced in stages by Fe and alkali. 

Ten parts NITROBENZENE and 7.5 parts Fe are heated to 90° and 3 parts conc. NaOH 
(containing some solid) are gradually added while temp. is kept at 100-110° by steam to produce 
azoxy BENZENE, further addition of some quantities Fe and NaOH forms azo BENZENE and when 
temp. is raised to fusion the hydrazo BENZENE that results may be poured off into molds to 
solidify. Residual paste on diln. gives oxides of iron valuable as pigment and NaOH, ante may 
be recovered. Reduction may be carried out in alc. or hydrocarbon solns. 


691,157—Jan. 14, 1902. Georg Mertinc, Germany. (Hochst.) 
Trimethyl hexahydrooxybenzylanilin and process of making same. 

Amino METHYLENE cyclo ketones such as anilino methylene dihydro iso PHORONE derived by 
treatment of corresponding ketone with NH,, are reduced to the hexahydro form, or trimethyl 
hexa hydro oxy benzyl ANILIN, in abs. alc. soln. by metallic Na. 


692,675—Feb. 4, 1902. Paul Junius and Akim Tuatscu, Germany. (Badische.) 
Diazo dye and process of making same. (Process not claimed.) 2-Amino phenol 
5-sulfo, diazo deriv. 
2-NITRANILIN 4-Sulfo is diazotized at 0°, Na,CO, in excess added and maintained at same 
temp. some hours, to form diazo 2-amino PHENOL 5-sulfo. 


692,676—Feb. 4, 1902. Paul Junius and Fritz GinrHER, Germany. (Badische.) 
Disazo wool-dye and process of making same. 2.6-Diamino phenol 4-sulfo. 
PHENOL 4-sulfo, dinitrated below 15° in mixed acids. is then reduced by Fe and acetic. 
693,67 0—Feb. 18, 1902. Karl ScHIRMACHER, Germany. (Hoéchst.) 
Disazo wool dye and process of making same. 2.4-Diamino phenol 6-sulfo. 


2.4-Dinitro PHENOL 6-sulfo is reduced. 


GROUP XXII.—INTERMEDIATES ; 341 


695,811—Mar. 18, 1902. Paul Juzius and Fritz GunrHER, Germany. (Badische.) 
Red azo dye. 1-Methyl sulfo 2-naphthylamin or ‘‘b-amino sulfo a-naphthyl methane.” 


1-Methyl sulfo 2-NAPHTHOL or oxy sulfo 1-naphthyl methane (D.P. 287,355) in dil. NH, coln., 
is made slightly acid to litmus with SO, then strong NH, added, heated in closed vessel at 
150-160° for 8 hours, and pptd. from soln. by HCl. 


695,812—Mar. 18, 1902. Paul Junius and Moritz JAHRMARKT, Germany. (Badische.) 
Chloranisidin. Chlor anisidin, m.p. 83°, acetyl deriv. m.p. 103°, ete. 


Nitro 4-dichlor BENZENE is dissolved in methyl] alc., solid KOH added, and refluxed to form 
nitro chlor ANISsOoL, which is boiled in dil. acetic acid with iron filings, excess carbonate added 
and distilled. 


700,670—May 20, 1902. Max BuicHnER, Germany. (Boehringer.) 
Electrolytic reduction of nitro or other compounds. 


Apparatus is shown and process described for reducing NITROBEZENE, 4-nitro TOLUENE, 
I-nitro NAPHTHALENE, phenyl NITROMETHANE, etc. The substance should be capable of being 
reduced by tin; the electrolyte must dissolve tin and a tin cathode is used with alcohol as 
solvent. Currents of high density (up to 1800 amps.) may be employed. 


700,671—May 20, 1902. Max Bicuner, Germany. 


Reduction of azo compounds. Azo compounds reduced by electrolysis using tin cathode 
and tin salt. 


In 700,670 a process is given for reducing nitro comps. to corresponding amino by 
electrolytic action with a tin cathode (or other indifferent cathode) and a fluid containing tin. 
A similar process is applied to azo bodies, in which case it is desirable to coat the cathode with 
layer of tin sponge, to maintain temp. at 60° and operate with lower current densities. 


700,672—May 20, 1902. Max BicHNer, Germany. 
Reduction of nitro compounds. Nitro compounds reduced by electrolysis using a 
cuprous salt in cathode electrolyte. 

Process is similar to 700,670 using copper metal or Cu,Cl, in cathode chamber with 
NITROBENZENE, and HCl (1 : 1) and Pt. cathode, and in the anode chamber 10 per cent H,SO, 
with anode of any suitable indifferent metal. Current of 1900 amps. per sq. meter is main- 
tained. Anilin HCl is the product. 

Note 700,671. 


702,171—June 10, 1902. Augustus BiscHLER, Switzerland. (Basle.) 
Process of making phthalic and benzoic acids. 


I- or 2-NAPHTHOL homolog or deriv., in 9 parts NaOH together with 9 parts CuO, is 
slowly heated to 240-270° and kept at that temp. till all CuO is reduced to Cu,O, residual alk. 
extracted with as little water as possible, diluted soln. filt., nearly neut. with mineral acid and 
saturated with CO, gas. Benzoic and phthalic acids in residue after evapn. to crystn. are sep- 
arated by usual methods. Less alkali may be used with larger proportion of CuO. 


704,490—July 8, 1902. Jean J. A. Tritzat, France. (Fries.) 
Composition for the production of vapors of formic aldehyde. 


Material containing FORMALDEHYDE is compounded with a neutral soluble substance such as 
NaCl or CaCl,, so that when dissolved the boiling point of aq. solvent is raised above 100°, 
vaporization is checked and when heated the formaldehyde vapors given off are free of moisture. 

Note 666,579. 


708,511—Sept. 9, 1902. Fritz Acu, Germany. (Boehringer.) 
Paramethyl-amidophenyl-glyoxylic acid and process of making same. 


Methyl aniLin alloxan is dissolved in 12 parts normal KOH and refluxed with 1.7 parts 
HgO until odor of NH, has disappeared, soln. filt., evap. to dryness, residue extracted with 
alcohol, etc. Homologs and derivs. claimed. 


704,825—July 15, 1902. Wilhelm Herzperc and Otto SIEBERT, Germany. (Berlin.) 


Red azo dye. 3-Toluylene diamin 4’-tolyl sulfonamid. 


2-Nitro 4-TOLUIDIN is condensed at 100° in aq. soln. with 1 mol. 4-ToLUENE sulfo chloride, 
gradually adding Na,CO,, and product reduced with Zn and HC), etc. 


342 DIGEST OF PATENTS 


709,151—Sept. 16, 1902. Richard Herz, Germany. (Hochst.) 
Blue sulfur dye and process of making same. 4-Amino 3-tolyl 4’-oxy diphenylamin. 


4-AMINO PHENOL and 1 mol. 2-ToLUIDIN are condensed in dil. sulf. acid soln. by oxidation 
with bichromate at low temp. then reduced in same soln. by heating to 85-90° with Na,S, filt., 
cooled and pptd. by NaHCO, or NaCl. Base is purified by soln. in HCl and repptn. with 
Na,CO,. Product is easily sol. in aq. containing mineral acids or alks., and in alc., diff. sol. 
C,H,, cryst. from latter as gray white needles, m.p. 160°. 


709,159—Sept. 16, 1902. Joseph Koerscuet, France. (Soc. Chim.) 


Ortho-sulfonated toluylic aldehyde and process of making same. 2-Sulfo 
toluyl aldehyde. 


3-TOLUYL ALDEHYDE, sulfonated at 0° in 10 parts H,SO, (60 per cent anhyd.) then let stand 
till temp. rises to 20-25°. 
Note 709,160 (VII). 


709,160—Sept. 16, 1902. Joseph Koetscuet, France. (Soc. Chim.) 
Green dye and process of making same. Sulfo acid of 3-toluyl aldehyde. 


3-Toluyl aldehyde is sulfonated by fuming sulf. acid (60 per cent anhyd.) at 0°. 


713,447—WNoy. 11, 1902. Paul Junius and Fritz GuntHER, Germany. (Badische.) 
Compound suitable for producing coloring-matter. 3.3’-Diamino 4.4’-dimethoxy 
diphenylmethane. 


2-Nitro ANISOL, 2 mols., is condensed with FORMALDEHYDE in conc. H,SO,, below 10° then 
reduced at 100° with Zn and acetic to diamino comp. Coupled with 2-NAPHTHOL product gives 
red tetrazo dye. 


%714,42S8—Nov. 25, 1902. Ernst Wirtu, Germany. 


Process of reducing aromatic nitro compounds. Complete reduction of nitro com- 
pounds by alkali sulfites. 


Compounds such as dinitro CARBAZOLE, dinitro DIPHENYLAMIN, or derivs., are ground with 
the calculated quantity of cryst. Na,S.gaq. and heated to roo® when reduction starts, at 130° 
is more energetic, at 150° about 90 per cent is reduced and at 160-170° reaction is complete, 
if closed vessels are used. 


715,748—December 16, 1902. Paul Bokessneckx, Germany. 
Process of making acetic acid. 


Apparatus is shown whereby an acetate mixed with a strong mineral acid, preferably HCl, 
is supplied continuously at the top of a series of receptacles, while a counter current of steam 
rises through these receptacles in order to heat the same and carry away the acetic acid, which 
is subsequently recovered from the steam by condensation. 


716,242—Dec. 16, 1902. Paul Junius, Germany. (Badische.) 
Disazo dye and process of making same. 4-Chlor 6-amino salicylic acid. 


SauicyLic acid is suspended in nitrobenzene at 50-60° and 1 equivalent of Cl gas added, 
product extracted from benzene with dil. carbonate soln., pptd. by acid, nitrated below 0°, the 
dry or moist press cake dissolved in carbonate soln. reduced by refluxing with bisulfite, and 
pptd. by acid. 


721,961—Mar. 3, 1903. Leo Marckwatp, Germany. 


Process of halogenizing organic fluids. MHalogenizing organic fluids, process and 
apparatus for regulating amount of halogen entering reaction. 


ToivoL or other in excess is treated with halogen, new portions being continuously acted 
upon and withdrawn from further action of halogen, by means of special form of apparatus. 


722,336—Mar. 10, 1903. Maurice C. M. Trxier, France. 
Process of obtaining tar extract. ) 


Tar (specially wood tar) is heated to 60-100°, alk. carb. added till effervescence ceases, 
extracted with cold aq., soln. pptd. by acid and redissolved in alkali. 


GROUP XXII.—INTERMEDIATES 343 


722,506—Mar. 10, 1903. Ludwig Hretmrrs, Germany. (Cordes.) 
Sulfonic-acid salt and process of making same. 

Resin oil is sulfonated in equal parts fuming H,SO,, soln. neut. with milk of lime, filt., 
satd. with CO,, evap. to small bulk, 2 vols. alc. added, filt., alc. removed by distn. and evap. 


to dryness, or after removal of alc. soln. is heated with H,O,, silver oxide or carbonate added, 
and soln. evap. in vacuum. 


722,507—Mar. 10, 1903. Ludwig Otto Hetmers, Germany. (Cordes.) 


Sulfonic-acid-salts of alkaline earthy metals and metals proper and proc- 
ess of making same. 


Resin oil sulfonated as in 722,506 is oxidized with H,O,, pptd. by milk of lime, etc., as in 
preceding patent. 


722,719—Mar. 17, 1903. Max KuceE., Germany. (Elberfeld.) 
Anthracene derivatives and process of making same. Anthraquinone phenox- 
azines. 


1-Nitro 2-oxy ANTHRAQUINONE or other nitro ortho-deriv., is condensed in glac. acetic acid 
with 4-TOLUIDIN or other aromatic amin to 1-toluidino 2-oxy ANTHRAQUINONE and chromic acid 
or other oxidizing agent added to this soln. Dark needles, sol. hot glac. acetic and boiling 
pyridin (V-GB), in conc. sulf. (BG), insol. in NaOH. 


722,861—Mar. 17, 1903. Ivan Lrvinstein and Carl Menscuinc, England. (Levinstein.) 
Benzylnaphthylamin-sulfonic acid and process of making same. Benzyl 
1-naphthylamin 4-sulfo. 
NAPHTHIONIC acid is boiled in strong aq. alk. carb. soln. to which sENzyt chlorid is added. 
Or components are heated to 30—50° in caustic alk soln. Product combines with diazo amino 
azo compounds to polyazo colors that are brighter and bluer than unbenzlyated compounds. 
Note 722,860 for derived dyes Group VI. 


724,078—Mar. 31, 1903. Albert BERTSCHMANN, Switzerland. (Basle.) 
Azo dye and process of making same. 3’-Amino benzoyl 2-amino 5-naphthol 7-sulfo. 
2-AMINO 5-NAPHTHOL 7-sulfo, in alk. carb. soln., containing sod. acetate is mixed with 3- 


nitro BENZOYL, chloride and the nitro compound reduced with Fe and acetic. Other components 
claimed. 


7 24,743—Apr. 7, 1903. Carl ScHIRMACHER, Germany. (Hochst.) 
Red azo dye and process of making same. 4-Nitranilin homo sulfo 2-amino 5-nitro 
benzyl sulfo, NH, salt. 


2-Chlor BENzyL chloride, is transformed by sulfite into 2-chlor BENzyL sulfo which is ni- 
trated in mixed acids, then heated with NH, to 150°. 


729,502—May 26, 1903. Martin Mozrst, Germany. (Hdéchst.) 
Uxidizing organic compounds. Oxidizing hydrocarbons to quinones by electric current 
with cerium as catalyst. 

Anthracene, NAPHTHALENE, phenanthrene, etc., are oxidized at 40-90° in lead lined vessel 
serving as anode in 20 per cent H,SO, containing 2 per cent cerium sulfate. Any indifferent 
metal may serve as cathode, if desired in form of agitator, with current up to 5 amps. and 2.9— 
3.5 volts. Further oxidation of NAPHTHOQUINONE gives PHTHALIC acid and of PHENANTHRA- 
QUINONE gives BENZOIC acid. 


729,876—June 2, 1903. Rudolph Lesser, Germany. 
Process of making substitution products of aromatic amins. 4-Nitranilin, 

s-nitro 2-amino benzoic, or other nitro or halogen aromatic amin by cheaper process. 

Phthal ANILIN or other phthalic anhyd. condensation product with aromatic amins, in 66° 
H,SO, soln., is nitrated below 3° and dried nitro deriv. heated at 170-180° with ANILIN in 
pressure vessel. Excess anilin and some 2-nitranilin are removed by steam, 4-nitranilin obtained 
by boiling aq. and the residue of phthalanilin is dried at 150° and used again. Similar processes 
are given for other comps. 


344 DIGEST OF PATENTS 


731,139—June 16, 1903. Arnold Sterner, Switzerland. (Basle.) 


Sulfo-acid of aromatic aldehyde and process of making same. Benzaldehyde- 
2.4-disulfo acid or other. 


TOLUENE or other, is converted by oleum to 2.4-disulfo acid and melt added to large excess 
fuming H,SO, (25 per cent SO,) containing powd. MnO, at 15-20°, kept at 30-35° for 48 
hours, poured on ice, bisulfite added to dissolve MnO,, then SO, and Mn pptd. by lime, Na 
salt formed, mineral salts pptd. by methyl alc., soln. conc. and aldehyde salt pptd. by ale. 


736,204—Aug. 11, 1903. Max Bicuner, Germany. (Boehringer.) 
Reduction of nitro and azo compounds, 

4-Amino azo BENZENE HCI is well mixed with 1.14 parts powd. electrolytic tin, 2 parts aq. 
and nearly 2 parts fuming HCl gradually added, heated until reduction is complete, drained 
from excess tin, poured into cathode space of electrolytic cell with diaphragm, and with cathode 
and anode of indifferent metals. At first a current of 1,800 amps. is used, later this is reduced. 
Tin is recovered as crysts. in about 94 per cent yield. Mother liquor is sat. with HCl to re- 
cover 4-PHENYLENE DIAMIN. Proportion of acid and Sn are such that only: SnCl, is formed. 
Apparatus is drawn and described. 


736,205—Aug. 11, 1903. Max BitcHner, Germany. (Boehringer.) 
Reduction of nitro compounds. Reduction by electrolysis using a catalyst. 

Process is similar to 700,670 using as catalyst Pb, Hg, Cr or Fe or their salts in acid soln. 
NITROBENZENE is reduced in presence of Pb, PbCl,, FeCl,, Cr (as cathode), ete. Apparatus is 
drawn and described. 


736,206—Aug. 11, 1903. Max Biicuner, Germany. (Boehringer.) 
Reduction of aromatic nitro compounds. Electrolytic reduction of nitro compounds 
in presence of alk. electrolyte and Cu. 
NitTROBENZENE, 2-nitro TOLUENE, 3-nitranilin, etc., is reduced, using powd. copper in cathode 
bath in suspension in conc. NaCl, in alc. NaOH, with BaCl,, etc., using Pt, Sn, Cu, Ni or other 
metal as cathode and carbon as anode. 


738,404—Sept. 8, 1903. Max Btcuner, Germany. (Boehringer.) 


Process of reducing nitro compounds. Reduction of nitro compounds with Cu and 
acid, and recovery of Cu. 


NITROBENZENE, 3-dinitro benzene or other, is refluxed with Cu and 38 per cent HCl and 
Cu recovered from waste liquor by electrolysis. 


ra 


741,552—Oct. 13, 1903. Franz ScuHouii, Germany. (Hochst.) 
Process of making azo dyes. 1.8-Azimino naphthalene 4-sulfo. 


1.8-Diamino NAPHTHALENE 4-sulfo is treated with nitrous acid. 


742,189—Oct. 27, 1903. Richard Herz, Germany. (Cassella.) 
Blue sulfur dye and process of making same. 4-Amino 3-methyl 4’-oxy 3/-chlor 

diphenylamin with Cl in ortho position to OH. 

2-Chlor 4-AMINO PHENOL in dil. sulf. soln. is mixed with 2-roLurp1Nn, cooled and bichromate 
soln. added, followed quickly by conc. soln. of Na,S, heated by direct steam to 85-002, filt. and 
pptd. by bicarbonate. 

Note Kohlropp, Liebigs Annalen, 234, page 5. 


742,797—Oct. 27, 1903. M. Mogst, H. Hertiern and E. Oppermann, Germany. (Héchst.) 
Electrolytic reduction of organic compounds by means of titanium com- 
pounds. 

A lead lined vessel serves as cathode and holds dil. H,SO, with about 2 per cent titanium 
sulfate. Circuit is closed and conc. soln. of nitro body such as 2-nitro 4-crEsot 6-sulfo, Na 
salt, is introduced at moderate temp. Diaphragm may be used but is not essential unless Cl 
is desired, when the anode compartment contains an acid soln. of NaCl. Azo BENZENE can be 
reduced to BENZIDIN in one operation. 


742,910—Nov. 3, 1903. Robert E. Scumipt, Germany. (Elberfeld.) 
Process of making anthraquinone alpha disulfonie acids. 


ANTHRAQUINONE is slowly heated to 130-140° in 2 parts fuming H,SO, (44 per cent SO,) 
with 1 per cent Hg,SO, as catalyzer. ANTHRAQUINONE 1.5-disulfo separates in crysts. Melt 


GROUP XXII.—INTERMEDIATES 345 


is cooled to 50° mixed with 66° H,SO, and disulfo acid filt. off, and 1.8-disulfo deriv. recovered 
from filtrate by pptn. with KCl. The 1.5 and 1.8 disulfo acids yield diamino or dialkyl diamino 
ANTHRAQUINONE when heated with NH, or METHYLAMIN, etc. 


743,664—Nov. 10, 1903. Robert E. Scumipt, Germany. (Elberfeld.) 
Anthraquinone-alpha-sulfonic-acid. Anthraquinone 1-sulfo acid, 

Fifty parts ANTHRAQUINONE in 60 parts fuming sulf. acid (20 per cent SO,) and 0.4 part 
Hg,SO, is heated to 150° for 45 min., diluted, unchanged anthraquinone filt. out, and K salt 
of sulfo acid pptd. from soln. by KCl. Straw yellow leaflets, diff. sol. in aq., soln. with HC 
and Zn (Y), forms alfa amino comp. with NH, at 180° and methyl amino deriv. with methyl 
amin at 170—180°. 


746,405—Dec. 8, 1903. Karl TuHun, Germany. (Elberfeld.) 
Purpurin-alpha-sulfoniec acid. Anthrapurpurin 5- or 8-sulfo. 

ANTHRAQUINONE 5- or 8-sulfo is heated at 30° in 15 parts fuming sulfuric (80 per cent 
SO,), separated and boiled in KOH soln. Sodium salt is red powd., sol. in aq. (YR), in NH,, 
NaOH and Na,CO, (R), in conc. sulf. (YR), with boric acid (VR); rEp (Al) or violet RED (Cr) 
acid mordant dyes. 


%755,801—Mar. 29, 1904. Robert E. Scumipt and Paul Tust, Germany. (Elberfeld.) 
Process of making alpha-oxyanthraquinone. 1-Oxy anthraquinone. 
ANTHRAQUINONE is sulfonated in presence of Hg or its compounds, as in 743,664, to alfa 


mono sulfo deriv. which is heated in an autoclave at 190° with dil. Ca(OH), soln., dissolved 
and pptd. by acid. 


757,057—Apr. 12, 1904. Robert E. Scumipt, Germany. (Elberfeld.) 
1-5-Nitroanthraquinone-sulfonie acid. 1-Nitro anthraquinone 5-sulfo, or amino and 
dimethyl amino derivs. 

ANTHRAQUINONE 1-sulfo in 96 per cent sulfuric acid soln. is heated to 80-90° with addition 
of HNO,. Crysts. of 1.5 acid separate while the 1.8 acid remains in soln., or alk. salts can be 
separated by pptg. soln. with NaCl. Nitration may be accomplished in nitric acid alone. Prod- 
ucts are cryst. plates, diff. sol. in aq. Reduction gives amino comp. and heating in aq. soln. with 
METHYL AMIN, the mono or di alkyl deriv. 


757,058—Apr. 12, 1904. Robert E. Scumipt, Germany. (Elberfeld.) 


1-S-Nitroanthraquinone-sulfonic acid. 1-Nitro anthraquinone-8-sulfo, mono or di- 
amino or dialkyl amino derivs. 

ANTHRAQUINONE 1-sulfo, obtained as shown in 743,664, in 96 per cent sulfuric acid soln., is 
nitrated by heating to 80-90° with HNO,, filt. to remove the 1.5 acid and 1.8 acid pptd. by dilu- 
tion with aq. Reduction yields the amino comp. from which the mono or dialkyl deriv. results 
by heating in aq. soln. with METHYLAMIN. ; 

Addition to 757,057. 


757,1836—Apr. 12, 1904. Martin Morst, Germany. (Hoéchst.) 
Oxidizing organic compounds. Cerium salts as catalysts for oxidations. 


Dil. H,SO, (15-20 per cent) containing 3-5 per cent ceric sulfate is heated to 60°, ANTHRA- 
CENE, NAPHTHALENE, etc., stirred in and temp. raised to 95°. Stronger acid gives more energetic 
oxidation with decompn. Other cerium salts may be employed. 


759,716—May 10, 1904. Paul Junius and Siegfried Harcxet, Germany. (Badische.) 
Red azo dye. 3-Chlor 4-toluidin 6-sulfo. 
3-Chlor 4-ToLurp1In sulfate is heated in 98 per cent sulfuric to 170-180°. 


761,998—June 7, 1904. Eduard Ritsert and Wilhelm Epstein, Germany. (Hochst.) 
Alkyl esters of 3-4 diamido-benzoic acid and process of making same. 

Ethyl 4-amino Benzorc acid is refluxed in glac. acrric acid containing anhyd. -sod. acetate, 
and when 67 per cent acetic is distilled residue is diluted with aq., saponified in dil. HCl, sep- 
arated crysts. purified, converted to nitro deriv. in HNO, (1.51) and product reduced with 
SnCl, and alc. HCl to ethyl 3.4-diamino benzoic acid. The formyl deriv. may be prepared from 
cone. formic acid and sod. formate. 


346 DIGEST OF PATENTS ° 


763,193—June 21, 1904. E. Marne, Germany. (Hoéchst.) 
sym-Dioxy 4.4/-diphenyl 6.6’-diamino diphenylamin m.p. 208°. 


(a) 4.4’-Diamino DIPHENYLAMIN is oxidized together with 2 mols. PHENOL, or (b) dipheny]l- 
amin is oxidized with 4-amino PHENOL or with QUINONE chlorimid, then reduced. 


765,201—July 109, 1904. Robert E. ScumMipt and Paul Tust, Germany. (Elberfeld.) 
Process of making anthrarufin.  1.5-Dihydroxy anthraquinone. 


I.5-ANTHRAQUINONE disulfo acid, sod. salt, made as in 742,910, is heated in autoclave to 180— 
190° with dil. Ca(OH), or other alk. earth hydroxide, cooled and pptd. by HCl. 
‘Note 765,637. 


765,576—July 19, 1904. Otto J. Graut, Germany. (Badische.) 


Process of making omega cyanmethyl-anthranilie acid. 


Moist ANTHRANILIC acid is mixed at common temp. or gently warmed with soln. of FORMAL- 
DEHYDE and separated product added to soln. of HCN, to which sufficient HCl has been added 
to free all HCN, warmed and stirred till solid forms. Ethereal or alc. solns. may be used, other 
cyanides, and for HCl, alk. sulfites or bisulfite. 


765,581—July 19, 1904. Paul Junius and Siegfried Harcxet, Germany. (Badische.) 
Azo dye and process of making same. 2.4-Dichlor 1-naphthylamin 7-sulfo. 


2.4-Dichlor acetyl 1-NAPHTHYLAMIN is dissolved in fuming sulf. acid (23 per cent SO,) 


below 45°, diluted and boiled to saponify. 


765,637—July 19, 1904. Robert E. Scumipt and Paul Tust, Germany. (Elberfeld.) 
Process of making ehrysazin. 1.8-Dioxy anthraquinone. 


1.8-ANTHRAQUINONE disulfo acid is heated in autoclave to 170-190° with dil. Ca(OH), or 
other alk. earth hydroxide, and pptd. by HCl. 
Note 765,201. 


769,593—Sept. 6, 1906. Louis Drescamps, France. 
Formaldehyde hydrosulfites and process of making same. 


FORMALDEHYDE or other body having aldehydic function, is caused to react with an alk., alk. 
earth or metallic hydrosulfite in molecular proportions, either in soln., as paste or in the dry 
state. 


775,570—Nov. 22, 1904. August L. Lasxa, Germany. (Oehler.) 
Dark-blue sulfur dye. (Process claimed.) 2/.4’-Dinitro 5-chlor 4-oxy 3-methyl dipheny]l- 
amin, m.p. 139-140°. 
6-Chlor 4-amino 2-crEsoL is refluxed with 2.4-dinitro chlor BENZENE in alc.-aq. soln. con- 
taining sod. acetate. 


776,264—Nov. 20, 1904. Albrecht Scumipt and Fritz BetumMann, Germany. (Héchst.) 
Blue sulfur dye and process of making same. Dimethyl 4’-amino 4-oxy 3-chlor di- 
phenylamin. 


PHENOL in alk. soln. is treated with Ca(OCl), to form 2-chlor PHENOL, filt., nearly neut., 
alk. filtrate mixed with dimethyl 4-PHENYLENE DIAMIN, or thio sulfo deriv. (from nitroso di- 
methylanilin), soln. being alk. so that chlor phenol remains dissolved, then at 10° oxidized by 
NaOCl to chlor 1nDOPHENOL, or thio sulfo deriv., filt., and reduced with Na,S to form diphenyl- 
amin comp. 


%78,477—Dec. 27, 1904. Karl Exiset, Germany, (Kalle.) 
Monochloro alpha-naphthol and process of making same. Chior 1-naphthol. 
I-NAPHTHOL in dil. alk. soln. is treated with 1 mol. NaOCl, then pptd. by HCl. White crysts. 
m.p. 64-65°, with characteristic odor, easily sol. in C,H,, alc. and ether. 
Note 778,478 for use of above Group VI. 


T78,772—Dec. 27, 1904. Wilkelm BruHAGEL and Gustav C. heheh rife Germany. (Badische.) 
Process of making hydroxyalkylanilin. 


ANILIN, 2 mols., is refluxed in aq. soln. with 1 mol. glycol cHLOoRHYDRIN, soln. made alk. 
and excess anilin distilled with steam. Other primary or secondary amins and other halogen 


GROUP XXII.—INTERMEDIATES 347 


derivs. of glycol hydrin can be employed and instead of excess amino comp. an alk. salt of a 
weak acid, such as sod. acetate or carb. 


779,860—Jan. 10, 1906. Arthur Lurrrincuaus, Germany. (Badische.) 
Violet sulfur dye and process of making same. 2.6-Dichlor indophenols. 
2.6-Dichlor 4-PHENYLENE DIAMIN or derivs. and 1 mol. PHENOL or deriv. are dissolved in 


dil. HCl, cooled to 0°, then bichromate and sod. acetate added. Resulting indophenol may be 
reduced to a diphenylamin. 


785,003—Mar. 14, 1905. Paul Jutius, Germany. (Badische.) 
Dichlor-dimethyl-fluorane and process of making same. 3-Chlor 4-cresol. 


3-Chlor 4-roLuIpIN sulfate is dissolved in 6 parts 25 per cent H,S0O,, 1 mol. NaNO, added, 
soln. distilled with steam and oxy deriv. recovered from distillate. 


785,003—Mar. 14, 1905. Paul JuLius, Germany. (Badische.) 
Dichlor-dimethyl-filuorane and process of making same. 
3-Chlor 4-crESOL mixed with equal parts PpHTHALIC anhyd. and ZnCl, is heated on oil bath 


at 185—190° for 8 hours. When cool, the dark mass obtained is digested at 100° with dil. NaOH. 
Dimethyl dichlor fluorene remains undissolved. 


792,600—June 20, 1905. Karl KrEKELER and August Branx, New York. (Elberfeld.) 
Reddish azo dye. 3’-Nitro or amino phenyl 5-oxy 7-sulfo 1.2-naphthimidazole. 


4-NITRANILIN aZ0 2-AMINO 5-NAPHTHOL 7-sulfo is condensed by boiling in dil. acid soln. with 
3-nitro BENZOyL chloride, or other. Amino comp. is obtained by reduction with Fe and H,SO,. 


793,559—June 27, 1905. Max Bazien and Theodor WouLFaHRT, Germany. (Badische.) 
Formaldehyde sulfoxylate and process of making same. 

FoRMALDEHYDE or other aldehyde and an alk., or alk. earth hydrosulfite, 1 mol. each, are 
heated in aq. soln. to 40° with o.5 mol. Ca(OH), or equiv. alkali, until mixture will no longer 
reduce indigo when cold. Soln. is evaporated in vacuum to cryst. out the alk. sulfite formed 
and residue is further evaporated. 


795,751—July 25, 1905. Oscar Batty, Germany. (Badische.) 
Compound of the anthracene series and process of making same. An alde- 
hyde condensed with a reduction product of anthraquinone. 


ANTHRANOL or other reduction product of anthraquinone or its derivs. in 30 parts 82 per 
cent sulfuric acid containing 1.5 parts BENZALDEHYDE or other aromatic alifatic aldehyde, is 
heated to 30-35° for 24 hours, diluted, and soln. extracted by ether. Products are insol. in 
dil. acids and alks., sol. in conc. sulf. (R-RBr), generally sol. in organic solvents. 


797,441—Aug. 15, 1905. Thilo KrorsEr and Carl JAGERSPACHER, Switzerland. (Basle.) 
Azo dye and process of making same. _ 1-Amino ‘2-acetoxy naphthalene 4-sulfo. 

1-AMINO NAPHTHOL 4-sulfo is dissolved in alk. carb. as basic salt and acetylated in aq. soln. 
by acetic anhyd. 


798,807—Sept. 5, 1905. August IL. Lasxa, Germany. (Oehler.) 
Indophenol sulfonic acids and process of making same. Indophenol sulfo acids. 

4-PHENYLENE DIAMIN sulfo acid and 1 mol. of a phenol such as 1.3-CRESOL, 1.2-cresol, 1-oxy 
naphthoic acid, etc., are condensed in alk. NaOCl soln. below 5° and resulting indophenol pptd. 
by salt. Sodium salts are dark brown powds., sol. in aq. (BV), bluer with NaOH, pptd. as 
indophenol sulfo acids by HCI (dark B). 


800,913—Oct. 3, 1905. Wilhelm Herzperc and Eduard Tuon, Germany. (Berlin.) 
Process of nitrating aromatie amins. Nitrating aromatic amins by cheaper process 
yielding a purer product. 

ToLvENE 4-sulfo 2/-toluidid, derived from 4-ToLUENE sulfo chloride and 2-roLuipIN, or other 
aryl sulfamid, is boiled in dil. HNO, for 6-8 hours. Use of expensive conc. acetic acid is 
avoided and a nearly chemically pure product obtained. 

23 


348 DIGEST OF PATENTS 


804,157—Nov. 7, 1905. Rudolf Miiier, Germany. (Hochst.) 
Process of making hydrosulfite preparations. (Product also claimed.) 


Alkali hydrosulfite and a ketone, such as dimethyl KETONE, are mixed in aq. soln. with caustic 
alkali and ammonia and mixture evaporated at low temp. in a vacuum. 


805,S890—Nov. 28, 1905. Otto Soust, Germany. (Hochst.) 


Diaminoformyl diphenylamin and process of making same. 4.4’-Diamino di- 
phenylamin by cheaper process. 


Dinitro formyl DIPHENYLAMIN, or acetyl deriv., mixed with aq., is slowly added to very dil. 
H,SO, containing Fe filings at 60-90° and kept at this temp. until suspended ppt. is black, not 
brown (4-5 hours), more acid added until H begins to evolve, filt., and pptd. by excess sod. 
acetate. Resulting diamino formyl DIPHENYLAMIN is hydrolyzed by boiling in dil. H,SO,. 


807,117—Dec. 12, 1905. Georg KatiscHEerR, New York. (Cassella.) 
Sulfo-acid and process of making same. Phenyl N-benzyl 1.2-naphthimidazol 5-oxy 
7-sulfo. 


1.2-Diamino 5-NAPHTHOL 7-sulfo is boiled in aq. soln. with 2 mols. BENZALDEHYDE. ‘The meta 
nitro or amino derivs. of benzaldehyde give products especially valuable for azo dyes. 


811,826—Feb. 6, 1906. Max Conrap and Walter Becky, Germany. 
Process of making 4-imino 2-6-dioxypyrimidin. 


Cyan acetic acid, ethyl ester, 1 mol. is mixed with 20 parts alc. in which 2 mols. Na have 
been dissolved, 1 mol. urEA then added and mixture refluxed for several hours. Soln. is neut., 
alc. distilled off, residue dissolved in aq. and pptd. by acetic acid. Or dry urea is mixed with 
sodamid and xyLon poured over it, then with cooling cyan acetic ester is poured over and temp. 
raised to 100—120°. 


Note 811,827-9. 


811,8S27—Feb. 6, 1906. Max Conrap and Walter Becxu, Germany. 
Process of making pyrimidin derivatives. 4-Imino 2.6-dioxy pyrimidin. 


Process is same as in 811,826 except that the acetyl deriv. of urea is employed. 


811,828—Feb. 6, 1906. Max Conrap and Walter Becky, Germany. 
Process of making pyrimidin derivatives. Alkyl 4-imino 2.6-dioxy pyrimidin. 


Process is essentially the same as 811,826 except that an alkyl or sym-dialkyl urREA is em- 
ployed. 


811,829—Feb. 6, 1906. Max Conrap and Walter Becky, Germany. 
Process of making pyrimidin derivatives. Alkyl 4-imino 2.6-dioxy pyrimidin. 


Process is similar to 811,828 using a di or trialkyl urea. 


812,124—Feb. 6, 1906. Emile A. Fourngaux, New York. (Metz.) 


Formaldehyde hydrosulfite and process of making same. Sodium formaldehyde 
sulfhydrate and basic zinc formaldehyde hydrosulfite (S$). 

Three parts zinc dust are mixed with boiling aq. to a paste, the remainder of 30 parts aq. 
added cold, SO, introduced until Zn. is dissolved (about 5 parts) keeping temp. below 45°, soln. 
cooled, ZnSO,, etc., filtered out, and a little more than 6 parts FORMALDEHYDE added, then very 
conc. soln. of Na,CO, (2 parts). Other methods are claimed and derivs. of other bases. 


814,031—Mar. 6, 1906. Emile A. Fourngaux, New York. (Metz.) 
Process of making zinc formaldehyde hydrosulfite, (S). Basic zinc formalde- 
hyde hydrosulfite, ZnSO,.CH,O.H,O. 


FoRMALDEHYDE bisulfite, derived as by-product from mfr. of zinc formaldehyde hydrosulfite, 
or by combining NaHSO, and CH,O in mol. proportion, is heated to 60° in aq. soln., Zn dust 
added, temp. raised to 80-90° and 1 mol. HCl or 0.5 mol. H,SO, run in below surface so slowly 
that it is never present in free state to any substantial degree, let stand and ppt. filt. out. 


Note 812,124. 


GROUP XXII.—INTERMEDIATES 349 


814,032—Mar. 6, 1906. Emile A. Fourngaux, New York. (Metz.) 
Process of making basic zine formaldehyde hydrosulfite, (S). 


A conc. soln. of 1 mol. FORMALDEHYDE, 1 mol. SO, and a little more than 1 mol. Zn dust 
is heated to 7o-100°. Basic zinc formaldehyde hydrosulfite separates as crysts. The order of 
adding components may be changed as shown by an example. 


820,052—May 8, 1906. Richard Kircuorr and Leo Krrkovius, Germany. (Berlin.) 
Violet-color lake and process of making same. 4’-Amino phenyl 3.8-disulfo 1.2- 
naphthyltriazol. 


4-NITRANILIN is coupled with I-NAPHTHYLAMIN 3.8-disulfo and resulting ortho amino azo 
comp. oxidized by PbO, to triazol, then NO, group reduced. 


823,435—June 12, 1906. Erich OprermMann, Germany. (Hochst.) 
Process of treating organic substances in presence of vanadium com- 
pounds. Electrolytic oxidation and reduction without diaphragm. 


Process is similar to 729,502 using different oxides of vanadium as catalysts. By varying 
current, temp., metals used as electrodes, the acid electrolyte and the oxide of vanadium em- 
ployed a large number of oxidations and reductions may be made, ANTHRACENES and ANILIN to 
quinones, etc., and azo BENZENE Or azoxy BENZENE tO BENZIDIN. 


828,741—Aug. 14, 1906. Max H. Ister, Germany. (Badische.) 
Anthraquinone aldehyde and process of making same, 2-Anthraquinone aldehyde. 
w-Dichlor or dibrom 2-methyl anthraquinone is heated to 130° in 97 per cent sulf. acid 
with or without boric acid. Products are sol. in conc. sulf. (Y-OR), in anilin (O-Y), in alc. 
and glac. acetic acid, in caustic (VR) and upon oxidization give carboxylic acids. 
Note 893,507. 


828,778—Aug. 14, 1906. Roland H. Scuoiit, Germany. (Badische.) 
Compound of the anthraquinone series and process of making same. 2.2’- 
Dimethyl 1.1’-dianthraquinone. 


1-lodo 2-methyl ANTHRAQUINONE, 2 mols. or other alfa halogen deriv., ground with copper 
powd., is heated in metal bath at 210° then at 270°, and copper and copper halogen removed 
by dil. HNO, Ag or other metal having power to withdraw halogen may be used for Cu. 
Greenish yellow to yellow brown powds. that may be recryst. from xylene and are sol. in 
C,H,NO,, C,H,NH, and conc. sulf. 


829,740—Aug. 28, 1906. Albrecht Scumipt, Germany. (Hochst.) 
Bordeaux-red sulfur dye and process of making same. Ethyl tolu-safraninone 
HCL 
4-Nitroso PHENOL, 4-amino phenol, etc., in neut. aq. soln. is. added to neut. soln. of ethyl 
3-TOLUYLENE DIAMIN, Na,CO, added, heated and oxidized with MnO, until blue color becomes 
red, filt., boiled and pptd. by HCl. 


833,513—Oct. 16, 1906. Otto DreFFENBACH, Germany. 
Manufacture of hydroazo derivatives. Electrolytic production of hydroazo derivs., 
using solvent to prevent solid deposits on cathode, etc. 


Cathode compartment of electrolytic vat is charged with 3 per cent NaOH and NiTrRoBEN- 
ZENE in benzene soln., anode compartment with 5 per cent NaOH, using Fe or Ni electrodes, 
current of 150 amp. hours, current density 2-4 amps. per sq. dem. cathode surface. Yield is 
80-85 per cent hydrazobenzene and 15-20 per cent azoxy benzene. The latter is changed to HCl 
salt and returned to cathode compartment. Other components and solvents claimed. 


833,605—Oct. 16, 1906. Paul Junius, Germany. (Badische.) 


Blue-red azo dye. 1.4-Dioxy naphthalene, ethyl ether. 
1.4-Dioxy NAPHTHALENE is refluxed in 3 parts alcohol containing 3 per cent HCl. Color- 
less needles, m.p. 105°. j 


839,360—Dec. 25, 1906. Wilhelm Bauer, Germany. (Bayer.) 


Red azo dye. Hydroquinone 4.’4”-diamino diphenyl diether, m.p. 170°. 
Hyprogurnone, K salt, is treated with 2 mols. 4-nitro chlor BeNnzENE, then reduced. 


350 DIGEST OF PATENTS 


841,999—Jan. 22, 1907. Rudolf MuLiEr and Woldemar Wo.LLenBeERG, Germany. (Hoéchst.) 
Process of making formaldehyde sulfoxylates. 
AcEetone and SO,, 1 mol. each, in aq. soln. are reduced with Zn dust at 50-60° and re- 


sulting ACETONE zinc sulfoxylate in aq. soln. treated with an equiv. of FORMALDEHYDE that dis- 
places the acetone, which is recovered. 


843,077—Feb. 5, 1907. Oscar Dresser and Myrtil Kann, Germany. (Bayer.) 
Azo dye.  5-Nitro 4-chlor 2-amino phenol. 


4-Chlor 2-amino PHENOL etheny] deriv., nitrated, saponified, and 5,4.2-product separated from 
isomeric 6.4.2- by fractional crystn. from alcohol, the former being more soluble. 


845,129—Feb. 26, 1907. Roland H. Scuort and Max A. Kunz, Germany. (Badische.) 


Process of preparing anthraquinone compounds. 2.2’-Dimethyl 1.1/-dianthra- 
quinone or derivs. by new process. 


1-Amino 2-methyl ANTHRAQUINONE in 97 per cent sulf. acid is diazotized, dild. with ice, 
the diazo sulfate filt., washed, dried, dissolved in acetic anhyd. with or without acetone and 
copper powd. added. (N evolved). Purified as in 828,778. 


848,791—Apr. 2, 1907. Leo WEBER, Germany. 
Pyrimidin derivative. (Process also claimed.) 2-Oxy pyrimidin. 

DICYANDIAMIN is condensed with negatively substituted acetic acid esters in which the 
cyan group, or the radical of acetic or malonic acid is present, by boiling in a soln. of an 
alcoholate to form 2-cyanimino 4-amino 5-diethyl 6-oxy PyRIMIDIN, which is decomp. into 2-oxy 
pyrimidin derivo., CO, and NH,, on prolonged boiling with dil. acids. 


851,423—Apr. 23, 1907. Michael Inyinsxy, Germany. 
Anthrachinone disulfonie acid. 1.7-Disulfo anthraquinone. 


ANTHRAQUINONE, or its 2-sulfo acid, is heated at 160° in 2 parts fuming sulf. acid (40 per 
cent SO,) containing 1.5 per cent Hg. Reactions of product differ from previous sulfo acids 
produced without Hg. (See table). Melted with lime a 1.7-dioxy anthraquinone (meta benz 
dioxyanthraquinone) is produced. 


8$51,444—Apr. 23, 1907. Oscar ScHuLtTHEss and Leo Kerxovius, Germany. (Berlin.) 
Amido-oxy-sulfonie acid of phenylInaphthimidazol and process of making 
Same. 3-Amino phenyl 1.2-naphthimidazol 5.7-disulfo acid. 
3-Nitro BENZALDEHYDE, the amino or other deriv., is condensed with 1.2-diamino NAPH- 
THALENE 5.7-disulfo (derived by reduction of azo comp. coupled in acid soln. with 2-NAPH- 
THYLAMIN 5.7-disulfo) and resulting BENZYLIDIN deriv. converted into imidazole by heating with 
acids and reducing agents. 


851,444—Apr. 23, 1907. Oscar ScuuiTHEss and Leo Krrxkovius, Germany. (Berlin.) 
Amido-oxy-sulfonie acid of phenylnaphthimidazol and process of making 
same. 


3-Amino phenyl 1.2-NAPHTHIMIDAZOLE §.7-disulfo is added at 130° to 2 parts KOH con- 
taining a little water and temp. slowly raised to 170°. Isomers and derivs. are claimed. 


861,397—July 30, 1907. Alexander Scumitz, Germany. 
Process of manufacturing fatty compounds for use as Turkey-Red oils. 
Modified Turkey-Red oil that will not form lime soaps with calcareous water. 
Castor oil is sulfonated as in the mfr. of Turkey-Red oil, is washed thoroughly and boiled 
either alone or with aq. until OH replaces sulfo group and an oxy fatty acid results. This is 


mixed in any proportion from 25-75 per cent with castor oil or other fatty oil or fat, heated to 
40-100°, cooled and sulfonated by usual method. 


869,07 3—Oct. 22, 1907. Ernst ERpMANN, Germany. (Berlin.) 
Para-aminodiphenylamin sulfonic acid and process of making the same. 
4-Amino-diphenylamin-4’-sulfo acid. 
4-Amino DIPHENYLAMIN is added to 3 parts sulf. acid monohyd. below 30° then heated at 
125° for 2-3 hours. With fuming acid less time is required and somewhat lower temp. Yield is 
75-80 per cent. 


GROUP XXII.—INTERMEDIATES 351 


871,507—Nov. 19, 1907. Benno Homo.ika and Josef Erser, Germany. (Hdchst.) 


Anthrachrysone derivatives. (Process also claimed.) w-Dialphyl diamino 2.6-dimethyl 
anthrachrysone and other alphyl amino derivs. 


ANTHRACHRYSONE, 1 mol. is dissolved in 1o or more parts of dil. NaOH, and at 20-25° 
2 mols. FORMALDEHYDE added, the separated garnet red cryst ppt. of the Na salt dissolved in 
a large amount of hot aq., is repptd. by a mineral acid as the free acid (OY) which is boiled 
with an excess of anilin or other amin. The two operations may be carried on as one or the 
formaldehyde may be first combined with the amin and then with anthrachrysone in alc. soln. 
Orange cryst. powd., insol. in aq., diff. sol. in organic solvents, decomp. on fusion, sol. in 
caustic (O), in mineral acids (Y). No claims as dye. 


871,600—Nov. 109, 1907. Hans Lasuarpt, Germany. (Badische.) 
Process of making formaldehyde hydrosulfite. Soluble form of zinc formaldehyde 
sulfoxylate. 


Zn dust is suspended in 15 per cent FORMALDEHYDE and SO, gas passed in at 20-50° until 
increase in weight shows that 1 mol. has been absorbed, then Zn is filt. out, soln. evapd. to sirup 
of ZnS,O,.2CH,O, which in aq. soln. with Na,CO, forms sod. formaldehyde hydrosulfite. Or 
if Zn salt is boiled with Zn dust, basic zinc formaldehyde sulfoxylate is formed. 


875,415—Dec. 31, 1907. Arthur Ercuencritn, Germany. (Bayer.) 
Process of generating formaldehyde. 


Com’l. FORMALDEHYDE soln. (40 per cent) is added to 0.5 parts of mixture of equal weights 
sod. perborate and NaOH. Reaction is lively and gaseous HCHO and steam are given off. 
Perborate alone will react and other peracids such as percarbonates, pertitanates, vanadates, 
uranates, zirconates, molybdates, etc. 


876,679—Jan. 14, 1908. Oscar Batty and Hugo Wo.rFft, Germany. (Badische.) 
Nitrobenzanthrone compound and process of making same. Nitrobenzan- 
thrones. 


BENZANTHRONE, benzanthrone quinolin or their sulfo acids, is nitrated in nitrobenzene or 
glac. acetic soln. to mono or dinitro product. According to conditions of temp., quantity of 
reagents, etc., the several mono nitro or dinitro derivs. are formed. Green yellow needles, 
m. p. 244°, sol. in conc. sulf. (Y), in 23 per cent oleum (R), on warming (BrG). 


885,566—Apr. 21, 1908. Max Bazien, Germany. (Badische.) 
Production of aldehyde sulfoxylates. 


FoRMALDEHYDE bisulfite is heated to 90-100° in aq. soln. with Zn dust without use of acid 
but in presence of zinc or ammonium sulfite, bisulfite or salt of formaldehyde sulfurus or hydro- 
sulfurus acid. 


885,567—Apr. 21, 1908. Franz Brcxer, Austria-Hungary. (Badische.) 
Production of aldehyde sulfoxylates. 


An ALDEHYDE, a bisulfite and a metal having reducing action are heated above 40° without 
acid, for instance, CH,O, NaHSO, and Zn in equiv. proportions. 


887,050—May 5, 1908. Bruno R. SerFert and Otto W. Meves, Germany. (von Heyden.) 
Sodium formaldehyde sulfoxylate. 


Quantities of SO, and FroRMALDEHYDE, between 1 and 2 equivs., will react with Zn dust to 
form mixtures of sulfoxylate and sulfite 1 gram of which will reduce from o0.8-2.2 gr. indigo. 
When one equiv. each of Zn dust and CH,O in aq., are treated with SO, gas until Zn is dis- 
solved, then with NaOH or Na,CO, and filt., the crysts. of Na salt obtained upon evapn., freed 
of crystal water, will reduce 1.9-2.2 times their weight of indigo. 


889,799—June 2, 1908. Walter Mirrscu, Germany. 
Process for the approximate separation of reaction products resulting from 
the sulfonation of aromatic bodies. 


To the undiluted sulfonating bath is slowly added NaCl or other alk. salt of a mineral acid 
while mixture is heated to 130-140° or higher if necessary until 2 layers of liquid form, that 
of the sulfo aromatic deriv. on top and of alk. bisulfate below. HCl gas escapes. Apparatus is 
drawn and described. 


ee DIGEST OF PATENTS 


891,753—June 23, 1908. Max C. von Unrunu, Germany. (Hansmann.) 
Oxidation of methane. Formaldehyde, etc., from methane, using oak bark at 30—-50° as 
catalyzer. 


One volume METHANE gas and 3 vols. oxygen, well mixed at 45.5° are passed slowly during 
12 hours through reaction vessel filled with oak bark pieces 2-3 mm. diam. For 48 liters mixed 
gases yield is 1,520 gr. FORMALDEHYDE and a little formic acid and methyl ale. Two vols. meth- 
ane and 15 vols. air under same conditions yield 1,565 g. formaldehyde and small amounts of 
other products. Temps. from 43—46.5° give more aldehyde, lower temps. more alcohol and higher 
temps. more acid. Methane in natural gas is preferred material. 


891,931—June 30, 1908. Carl HrmpENREICH, Germany. (Bayer.) 
Blue azo dye. 4-Amino 3-chlor dialkyl anilin. 


3-Chlor dimethyl ANILIN is converted to nitroso compound and reduced. 


893,507—July 14, 1908. Max H. Isiter, Germany. (Badische.) 
Omega-halogen-methyl-anthraquinone compound. (Process also claimed.) w- 
mono, di or trihalogen 2-methyl anthraquinone. 


2-Methyl ANTHRAQUINONE is heated at 170° in an autoclave with 2 or more mols. bromine 
or chlorine, SO,Cl,, or other halogen, preferably using iodine, etc., as catalyst. White cryst. 
comps., sol. in glac. acetic; dichlor deriv. with m.p. 200°. 


8§94,148—July 21, 1908. Georges ImpBEert, Germany. 
Process of producing dichlor-ethoxy-ethylene. Dichlor ethoxy ethylene. 
ALCOHOL, 94 per cent, is boiled 12 hours with NaOH and CaO and when slightly cooled, 


trichlor ETHYLENE carefully added, again boiled, and product distilled with steam. 
Note 894,149. (Indigo group.) 


902,150—Oct. 27, 1908. Carl HrerpenreicH, Germany. (Bayer.) 
Para-aminoacetyl meta-toluidin. Acetyl 4-amino 2-toluidin. 

ANILIN is coupled with 3-ToLuIpIN, soln. made alk., excess toluidin driven off with steam 
and residue heated at 90-100° with 1 mol. acetic anhyd. ‘The resulting solid mass is pulverized 
and slowly stirred into boiling aq. containing Fe filings, anilin is removed by steam, liquid made 
alk., filt. and product salted out. 


902,895—Nov. 3, 1908. Bertram Mayer and Alfred ScHaarscumipt, Switzerland. (Basle.) 


Orange-to-yellow wat dye and process of making same.  w-Dichlor-2-methyl 
anthraquinone. 


2-Chlor TOLUENE is condensed with pHTHALIC anhyd. and AICI,, then the resulting 2-chlor 
toluyl BENzoIC acid heated in sulfuric acid. 


903,588—Nov. 10, 1908. Otto LieBKNEcH'T, Germany. (Scheideanstalt.) 
Manufacture of sodium arylamins. 


Twenty parts ANILIN are heated to 140°, then about 0.7-1.3 per cent NiO, and 3 parts metal- 
lic Na in portions, added carefully. Other aryl amins and a variety of catalysts are claimed. 


910,648—Oct. 7, 1902. Alfred Wout, Germany. 
Process of making acetyl chlorid. ; 


Gray calcium acetate (AcETIc acid, Ca salt) ot 80 per cent strength or other alk. earth ace- 
tate and about 0.5 parts (cc) sulfuryl chloride are ground together in ball mill for 8-10 hours 
keeping temp. low and product distilled or extracted with hydrocarbon solvent. Yield is over 
80 per cent. Shorter time of grinding will give lower yield. 


916,161—Mar. 23, 1909. C. JAGERSPACHER, Switzerland. (Basle.) 
Azo dye and process of making same. 4’-Amino 1’.2’-azimino phenyl 2-amino 5-naph- 
thol 7-sulfo. 
2-NAPHTHYLAMIN 5.7-disulfo in aq. sod. acetate is refluxed with 2.4-dinitro chlor BENZENE 
to form 2’.4/-dinitro phenyl 2-naphthylamin 5.7-disulfo, the ortho nitro group reduced in alc. 
soln. with Na,S and NH,Cl, converted by NaNO, to azimino comp., reduced, then heated in 
autoclave at 190—200° with dil. NaOH to form naphthol. 


‘on en 


GROUP XXII.—INTERMEDIATES 353 


921,546—May 11, 1909. 
P. Juuiius, E. FussENEccER and L. Biancry, Germany. (Badische.) 
Azo dye and process of making same. _ 5-Chlor 4-methyl 2-nitranilin, m.p, 159°. 


5-Chlor 4-methyl AcETANILID (or 4.5-deriv.), is nitrated, saponified, and impurity in the form 
of (4.3.2) comp. separated by its solubility in alc. 


935,815—Oct. 5, 1909. Ferdinand RapEMACHER, Austria-Hungary. 
Process of preparing zine formaldehyde sulfoxylate. 
FoRMALDEHYDE bisulfite is converted to Zn formaldehyde sulfoxylate by treatment at 90—100° 


with Zn dust and a zinc salt such as acetate, chloride, sulfate, etc. When in conc. soln. product 
is a stiff paste and when diluted the zinc salt separates and may be filt. out. 


943,560—Dec. 14, 1909. Eduard Miincu, Germany. (Badische.) 
Thiosalicylic compound and process of making same. _ Thio salicylic acid. 


ANTHRANILIC acid is diazotized and run into aq. soln. of sulfur in Na,S below 5°, acidified, 
filt., freed from S. by soln. in carbonate, again filtered, then pptd. by acid. 


953,049—Mar. 29, 1910. Julius Mocrensurc, Germany. (Bayer.) 
Process of making 1.8-diaminonaphthalene-4-sulfonie acid. 1.8-Diamino naph- 
thalene-4-sulfo or ‘‘S” acid. 


1 8-Diamino NAPHTHALENE is stirred into strong sulfuric acid till crumby, then ‘“‘baked’”’ at 
155° in vacuum. 


958,912—May 2.4, x10. Karl Exset, Germany. (Kalle.) 
Nitro-ortho-oxy-azo ¢elors and process of making same. Zinc salt of nitrated 
diazo 1-amino 2-naphthol 4-sulfo, or other comp. whereby pure nitro azo oxy colors may be 
produced. 
I-AMINO 2-NAPHTHOL 4-sulfo is diazotized and pptd. as zinc salt, dried, pulv., nitrated at 
low temp. and again pptd. by ZnSO,, then dried and preserved as diazo salt. 


993,915—May 30, Io1l1. Fritz ULLMANN, Germany. (Berlin.) 
Halogenized carboxylic acid of the phenylaminoanthraquinone series. 
4’-Brom 2/-carboxy 1-anilino anthraquinone. 


1-Chlor ANTHRAQUINONE is condensed with 1 mol. 4-brom ANTHRANILIC acid or other halo- 
genated deriv., by heating to 160° in amyl alcohol with copper acetate or copper and sod. ace- 
tate (to absorb HCI and perform catalytic functions). Violet powds., insol. alc. and C,H,, sol. 
in pyridin. 


994,420—June 6, 1911. Re. 13,304—Oct. 3, 1911. Wilhelm NEELMEIER, Germany. (Bayer.) 
Aminobenzoylaminobenzoyl-2-amino-5-naphthol-7-sulfonie acid. 2”-, 3”- or 
4”-Amino benzoyl 3’-amino benzoyl 2-amino 5-naphthol 7-sulfo. 
3’-Amino benzoyl 2-AMINO 5-NAPHTHOL 7-Sulfo is heated to 50—60° in dil. carb. acetate soln. 
with 3-nitro BENzoyL chloride, product reduced with Fe and acetic, filtered, made acid to ppt. 
free sulfo acid, etc. 


999,062—July 25, 1911. Fritz Sincer, Germany. (Griesham.) 
Manufacture of anthranol, Anthranol and dianthrene. 


ANTHRAQUINONE, powd., is heated in autoclave with 50 per cent FeCl, soln. containing Fe 
powd., cooled, filt., dissolved in NaOH and pptd. by HCl. Other solvents and reducing agents 
claimed. Heating anthranol soln. with FeCl, gives dianthrene in one process. Anthranol, m.p. 
152°, is sol. in NaOH (Y) and cryst. from dil. acetic in needles. 


1,003,289—Sept. 12, 1911. Eduard Muncu, Germany. (Badische.) 


4.4/-dibrom-diphenyl-disulfid-2.2/-dicarboxylic acid and process of obtain- 
ing such bodies. 4.4’-Dibrom diphenyl disulfid 2.2’-dicarboxylic acid. 


s-Brom ANTHRANILIC acid, derivs. or analogs, in dil. NaOH soln. is mixed with nitrite 
and poured into excess acid at 0° to form diazo deriv., which is added to soln. of Schlippe’s 
salt (sodium sulfantimoniate Na,SbS,.9 aq.) or corresponding Sn or As salt, pptd. with acid, 
filt., dissolved in (NH,),CO, and again pptd. by acid. A colorless product, m. p. 310°, when 
freshly pptd. easily sol. in acetone, diff. sol. alc., glac. acetic, and aq. 


354 DIGEST OF PATENTS 


1,005,176—Oct. 10, 1911. Paul Euriticu and Louis Benpa, Germany. (Cassella.) 

3.6-Diaminoacridinium and its salts. 3.6-Diamino acridin, SnCl, double salt. 
4.4’-Diamino DIPHENYLMETHANE is added to 66° H,SO,, cooled, HNO, added and temp. held 

at 8-10° for 2-3 hours, neut., made strongly alk. and separated product reduced with HCl and 


gran. Sn. (temp. rises to 110°). Clear soln. heated at 135° 4 hours in autoclave, cooled and tin 
double chloride of diamino acridin filtered out. It forms a yELLOW basic mordant dye. 


1,006,793—Oct. 24, 1911. Franz Rieruor, Austria-Hungary. (Blumberg.) 
Process of producing aldehyde sulfoxylates. Aldehyde sulfoxylates by shorter 
process. 


FORMALDEHYDE, a bisulfite, Zn and aq. are mixed in a digester and caused to react by ap- 
plication of 6-8 atoms. pressure without external heat for less than an hour in atmosphere of 
CO, gas. Apparatus shown and described. 


1,010,177—Noyvy. 28, 1011. Friedrich Rascuic, Germany. 


Process for the manufacture of alkali earth salts of hydroxlyamin disul- 
fonie acid. 


One part Ca(NO,), soln. (10 N) is mixed with 40 parts CaH,(SO,), soln. (N,) and 1 part 
H,SO, (10 N) added below 10°. SO, is liberated, CaSO, is pptd., leaving Ca(SO,), NOH in 
liquid. Sodium comp. may be produced by similar process but is more costly. 


1,013,181—Jan. 2, 1912. August Kiaces and Hermann Vo.isperc, Germany. 
Process of making chlorosulfonic acid. 


Chlor sulfonic acid containing SO, is cooled to 0° and HCl gas introduced, keeping temp. 
below 30°, or mixed SO, and HCl gases may be passed into the solvent. Air may be present 
so that it is possible to use the 7 per cent SO, air mixture coming directly from the contact ap- 
paratus, a tower similar to Glover or Gay Lussac being used for the absorption. 


1,014,039—Jan. 9, 1912. Melchior Bénicer, Switzerland. (Sandoz.) 
Dark-blue monazo dyestuffs. (Process also claimed.) Brom 1-amino 2-naphthol 4-sulfo. 


Diazotized 1-AMINO 2-NAPHTHOL 4-sulfo is dissolved at 50-90° in conc. or fuming H,SO, 
through which Br vapor is passed using iodin as carrier, or in chlor sulfonic soln. 

Note process in 1,014,114 using chlor sulfonic acid and bromin. Patent does not claim 
above compound. 


1,014,114—Jan. 9, 1912. Melchior BénicEr, Switzerland. (Sandoz.) 


Red monoazo dyestuffs. (Process also claimed.) Brominated 1-amino 2-naphthol 4-sulfo, 
diazo deriv. 


Diazotized I-AMINO 2-NAPHTHOL 4-sulfo in chlor sulfonic acid soln. is refluxed at 55-—60° 
with bromin. HBr is generated and reacts with excess chlorsulfonic to form SO, and Br so 
that less than theoretical quantity of Br is required. 

Note process in 1,014,039. 


1,016,092—Jan. 30, 1912. Gustav RetnicKE, Germany. (Berlin.) 


Process of producing para-alkyloxyphenylethylamins and their N-alkyl 
derivatives. 4-Methoxy phenyl w-ethylamin and homologs. 


4-Methoxy PHENYL ethyl alcohol is mixed with equal volume dry CHCl, and PCl, gradually 
added then temp. raised to 100°, excess CHCl, and POCI, driven off and residue. heated at 100° 
with 30 per cent alc.-NH, in closed vessel. Volatile parts are eliminated by distn. from alk. soln. 
and product extracted by ether. Alkyl derivs. are claimed. 


1,022,019—Apr. 2, 1912. Hans Bucuerer, Germany. (Kalle.) 
Amino-oxy-naphthalene sulfonic acid asd process of making same. 2-Amino 
s-naphthol 1-sulfo. 


2-NAPHTHYLAMIN 5.1-disulfo is added to 2 parts fused KOH at 150°, and heated further to 
210-230°. No water is added to melt. Product yields soluble azo dyes when combined with 
a diazo body in alk. soln., and a diff. sol. dye when soln. is acid. 


1,023,758—Apr. 16, 1912. Friedrich Rascuic and Max Korsner, Germany. (Raschig.) 
Process for the manufacture of chlorinated phenol esters and of oxybenzyl 
alcohols, oxybenzaldehydes and oxybenzoie acids. 


GROUP XXII.—INTERMEDIATES 355 


2.2/-DICRESOL carbonate from COCI, and cresou is treated with 1 mol. Cl gas at 180° and 
product distilled at 247° and 30 mm. pressure. Upon exhaustive saponification the resulting 
w-dichlor deriv. gives salicylic acid, 80 per cent yield. When 2 or 3 mols. Cl are added the 
products are oxy benzaldehyde or benzoic acid. Phosphorous acid esters from POCI, and phenols 
will give same products. 


1,024,308—Apr. 23, 1912. Hans Bucuerer, Germany. (Kalle.) 
Manufacture of azo coloring-matters containing a carbazole derivative. 

(Product also claimed.) 5-Oxy 7-sulfo 1.2-naphthcarbazol, or other. 

2-AMINO 5-NAPHTHOL 7-sulfo “I” is refluxed in NaOH soln. containing bisulfite with PHENYL, 
hydrazin until “I’’ acid has disappeared, excess hydrazin distilled off from strong NaOH soln. 
and SO, removed by boiling with acid. Other components claimed. 

Note D. P. 208,960 for further description of process. 


1,028,521—June 4, 1912. Arthur ZitscHerR and Ernst J. Ratu, Germany. (Griesheim.) 
Anthracene derivatives and process of making same. (Products not claimed.) 
2-Anthramin. 
2-Amino ANTHRAQUINONE, 2-amino anthranol, or amino or halogen derivs. which do not 


contain sulfo group, is refluxed in ro parts NH, soln. (0.91) or with 7 parts NaOH, (35°), 
and 2 parts Zn dust for 8-15 h. until insol. in alkali. 


1,043,873—Nov. 12, 1912. Franz Scuoit and Willy Trorrp, Germany. (Héchst.) 
Brown azo dyestuff and process of making same. 4-Amino 3’-sulfo N-phenyl azi- 
_mino benzene. 


2.4-Dinitro chlor BENZENE is condensed with ANILIN 3-sulfo and nitrous acid to form nitro 
azimino comp. which is reduced. 


1,045,196—Nov. 26, 1912. Karl ScurtrMAcHER, Germany. (Hochst.) 
Azo dyestuff. %S-Amino 4-methyl diphenyl sulfone. 


4-TOLUENE sulfo chloride is condensed with BENZENE, nitrated and reduced. 


1,059,670—Apr. 22, 1913. Georg Housts, Germany. (Bayer.) 
Dye. 4”-Amino benzoyl 4’-amino benzoyl diamino stilbene disulfo, or other. 

Diamino sTILBENE disulfo is dissolved in hot Na,CO, soln. to which melted 4-nitro BENZOYL 
chloride is added, product reduced with Fe and acetic, neut. by soda, filt., and pptd. by salt, 
again dissolved in hot aq., more finely powd. or melted 4-nitro benzoyl chloride added, and again 
reduced. Other components claimed. 


1,062,350—May 20, 1013. Kurt H. Meyer and Friedrich Brereius, Germany. 
Process for the manufacture of monovalent phenols from mono-chloro sub- 
stitution products of aromatic hydrocarbons. Replacing Cl with OH by water 
at 300° under pressure. 
CHLORBENZENE when heated at 300° with 4 parts aq. under pressure gives a 5 per cent 
yield of phenol. When 1o per cent soda is present the yield is 70 per cent. 1-Chlor naphthol 
in 3 parts 10 per cent soda soln. gives a 50-60 per cent yield. 


1,066,777—July 8, 1913. Arthur ZritscuHer and Ernst J. Ratu, Germany. (Griesheim.) 
Process of making nitro-amino derivatives of the anthraquinone series. 
Nitro amino anthraquinones. 
1-Nitro amino ANTHRAQUINONE is stirred 1 hour at common temp. in 1o parts conc. H,SO, 
or other nonnitrating mineral acid, in absence of nitratable substances, poured on ice, and 
mixed 1-amino 2- or 4-nitro ANTHRAQUINONE recovered as a red ppt. Reduction with Na,S gives 
diamino anthraquinone. 


1,075,171—Oct. 7, 1913. Albrecht Turete and Georg WicumMann, Germany. (Berlin.) 
Process for the manufacture of 2-phenylquinolin-4-carboxyliec acid. Im- 
proved yield of 2-phenyl quinolin-4-carbo acid. 

ANILIN is added at 40-50° to equimol. of BENZALDEHYDE, solid mass drained and residual 
aq. distilled off in vacuum. Resulting benzylidene ANILIN is heated to boiling in strong alc. and 
1 mol. PyRORACEMIC acid added. Or the anilin and benzaldehyde are together dissolved in alc., 
boiled 2 hours, and pyroracemic acid gradually added. 


350 DIGEST OF PATENTS 


1,083,051—Dec. 30, 1913. Johann Boner, Germany. (Badische.) 
Producing anthraquinone compounds. Anthraquinone and sulfo, chlor or other 
derivs. 


ANTHRACENE or deriv. is added to mixture of 4 parts C,H,NO, or other liquid of the aro- 
matic series and 1.2 parts N,O, at 15°, let stand few hours then slowly heated to 100°. 


1,083,489—Jan. 6, 1014. Wilhelm HaHNENKAMM, Germany. (Hdochst.) 
Sulfur dyestuffs and process of making same. Indophenol sulfonic acid. 


4-PHENYLENE DIAMIN, benzidin, or other para diamin, is heated together with 1-NAPHTHYL- 
AMIN 7-, 8- or 2-sulfo and product a) oxidized with 4-amino PHENOL or derivs. or b) con- 
densed with nitroso PHENOL or derivs. (see lists) to give a quinoid. 


1,085,708—Feb. 3, 1914. Wilhelm Srrer1nxopr, Germany. 
Process of producing sulfur derivatives of hydrocarbons. Synthesis of thio- 
phene, etc. 


Finely powd. pyrites in an iron tube provided with an endless screw, is heated to 300-320° 
for 6 hours, and ACETYLENE gas led over at the rate of 120-140 liters per hour with renewal 
of pyrites. Gaseous products consisting of hydrogen, acetylene, and sulfur derivs. are ab- 
sorbed in paraffin and recovered as 41 per cent thiophene, 4o per cent higher sulfur derivs. 
ete; 


1,099,761—June 9, 1914. Leopold OstERMANN, Germany. 
Process for the formation of diaryl ethers. Diaryl ethers by cheaper process. 


PHENOL is combined with KOH to a phenolate, dried and dissolved in about equal parts 
phenol together with 1 mol. chlor BENZENE and heated at 200-220° in an autoclave. Un- 
consumed chlorbenzene and diphenyl ether are expelled from product by steam and redistilled. 
Other aromatic halogen derivs. and dry phenolates will give ethers in good yields by similar 
process. 


1,101,111—June 23, 1914. Arthur ZitscHer, Germany. (Griesheim.) 
Process of making the arylamids of 2.3-oxynaphthoie acid. 2-Oxy 3-naphthoic 
acid anilid. 


2-Oxy 3-NAPHTHOIC acid and ANILIN, 1 mol. each, are refluxed in toluene soln. with PCI, 
until no free amin can be detected, made alk., toluene expelled by steam, and anilin filt. out. 
Other aryl amins, condensing agents and indifferent solvents claimed. 


1,101,778—June 30, 1914. Wilhelm Bauer, Alfred Herre and Rudolf Mayer. (Bayer.) 
Vat dyestuffs. o-Chlor naphthisatin. 


1.1/-Dichlor cyano carbo 2.2/-DINAPHTHYLIMID is treated with anhyd. AICI, and saponified. 


1,103,383—July 14, 1914. Fritz SincER and Ernst Minarcu, Germany. (Griesheim.) 
Process of making anthraquinone. Anthraquinone by oxidation with nitric acid. 


ANTHRACENE (85 per cent) is suspended in nitrobenzene, glac. acetic, or other non- 
reactive solvent, HNO, (31 per cent) added, and mixture heated to 35° or other temp. under 
60°, impurities removed by filt. and HNO, recovered. More HNO, (48°) is added to nitrobenzene 
soln. which is heated to 105° (above 60°) until evolution of red vapors ceases. Resulting an- 
thraquinone has m. p. 278-281°. Process is compared with former patents with related ma- 
terials. 


1,104,943—July 28, 1914. Rudolf UHLtENHUTH, Germany. (Hoéchst.) 
Process of producing amino-anthraquinones. Amino anthraquinones. 


ANTHRAQUINONE 2-sulfo, Na salt, or other deriv., mixed with BaCl, soln., is heated at 
170-177° with excess 25 per cent NH, for 48 hours under pressure. BaCl, or an equivalent 
metallic salt, absorbs the SO, liberated in the reaction, forms an insol, salt and a larger yield 
of amino anthraquinone results. 


1,119,546—Dec. 1, 1914. Fritz Sincer, Germany. (Griesheim.) 
Process of making anthraquinone. Anthraquinone by oxidation with HNO, and Hg 
as catalyst. 


Method is same as in 1,103,383, applying HNO, in two stages, difference being in use of 
Hg as catalyst and in the removal of organic salts of the latter by introducing Cl vapor at the 
end of the process. 


GROUP XXII.—INTERMEDIATES so7 


1,126,413—Jan. 26, 10915. Kurt Drsamari, Germany. (Synthetic.) 
Azo dyestuff. Aceto acetanilid-4-carbo acid. 


4-Amino BENZOIC acid, ethyl ester, in naphtha soln., is boiled with aceto ACETIC ESTER, then 
saponified in dil. alc. soln. 


1,128,369—Feb. 16, 1915. 
Albrecht Scumipt, Gustav KronLEIN and Ernst RuNNE, Germany. (Hochst.) 
Carbazol-sulfonic acids and process of making same. Mono sulfo carbazole and 
derivs. for mfr. of indophenol dyes. 


CARBAZOLE, or its methyl or ethyl deriv. is mixed with 15-20 parts nitrobenzene or other 
indifferent solvent, and about 0.5 parts fuming H,SO, (20 per cent SO,) gradually mixed in 
while cooling. Nitrobenzene is separated by adding water and sulfo deriv. recovered from aq. 
soln. 

Note 1,128,370. 


1,128,370—Feb. 16, 1915. Albrecht ScuMipt and Gustav KroniEin, Germany. (Hochst.) 
Indophenolsulfonie acid and process of making same. 

CarBAZOLE sulfo acid or homolog made as in 1,128,369 in 10 parts conc. H,SO, is mixed 
with 1 mol. 4-nitroso PHENOL or deriv., also in 10 parts H,SO,, diluted with ice and pptd. 


with NaCl and Na,CO,. Or instead of a nitroso comp. 4-amino PHENOL and an oxidizing agent 
such as MnO, can be used. 


1,128,813—Feb. 16, 1915. Wilhelm NEELMEIER and August S1cwart, Germany. (Synthetic.) 
Azo dyes. 2-Naphthol 6-sulfonyl phenyl ether. 


1-Carbo 2-NAPHTHOL 6-sulfonyl chloride, condensed with phenol, and carbo group split off, 
or it may be eliminated in later processes of combination. No details given. 


1,140,747—May 25, 1915. Myrtil Kaun and Anton Ossenpeck, New York. (Syn.) 
2.3-Oxynaphthoiec-acid derivative. 2/-Oxy 3’-naphthoyl 2-amino 7-naphthol. 


2-Oxy 3-NAPHTHOIC acid is suspended in solvent naphtha with 1 mol. 2-AMINO 7-NAPHTHOL, 
PCl, added slowly and refluxed. Other amino naphthols claimed. 


1,173,550—Feb. 29, 1916. Carl Boscu, Germany. (Badische.) 
Manufacture of urea. 


Ammonium comps. with CO, are heated in closed vessel, urea separated and the unconverted 
NH, comps. are recovered by distilling below 80° until urea is dry. 


1,219,166—May 13, 1917. Julius Scuomiptin and Max Fiscuer, Germany. 


Manufacture of chlorinated products of xylene, aldehydobenzoie acids and 
dyestuffs therefrom. Trichlor aldehydo 3-benzoic acid, or other. 


Current of chlorine gas is passed into 2-, 3-, Or 4-XYLENE (tech) while cold and in the 
dark, then in the light at 120° to definite increase weight or density Product is then heated 
in conc. sulfuric to 90-100°. 


1,228,414—June 5, 1917. Louis M. Dennis, New York. 

Method of separating an aromatic-sulfonic acid from sulfuric acid and of 
obtaining the sulfonic acid in solid form. Naphthalene 2-sulfo acid, or other, 
in solid form. 


Mixture of acids and sulfonic acid of sulfonating bath is treated with a solvent for the 
sulfo acid, of greater solvent power at high temps., such as toluene, solvent separated and 
cooled. 


1,238,932—Sept. 4, 1917. Paul Nawiasxy, Germany. (Badische.) 


Anthraquinone compound. (Process also claimed.) 2-Phenyl amino anthraquinone or 
anthraquinone-2-arylamins. 


ANTHRAQUINONE 2-sulfo acid, Na salt, or deriv., is heated in dry ANILIN, or other aro- 
matic amin with caustic alkali and oxidizing agent, such as air. Products are insol.. in aq., alks., 
acids, sol. in organic solvents and conc. sulf., the latter soln. when heated turning to blue 
or blue violet. 


358 DIGEST OF PATENTS 


1,273,901—July 30, 1918. Gilbert T. Morcan, England. 


Process for the manufacture of para-amino-N-methylformanilid. (Product 
also claimed.) 4-Amino N-methyl formanilid. 


N-Methyl FoRMANILID is dissolved in conc. sulf. acid, mixed nitro-sulfuric is added below 18° 
to form para nitro deriv. which is reduced by Fe borings in dil. aq. formic acid at 100° so 
as not to eliminate formyl group. Iron is pptd. by CaCO,, and hot filtrate cooled or concentrated 
and cooled to crystn. 


1,274,503—Aug. 6, 1918. 
Carl Breacu, Alwin Mitrrascu and Carl NeresHeimer, Germany. (Badische.) 


Manufacture of urea. 


Ammonium carbamate, derived from CO, and NH,OH under pressure, is combined with 
10-20 per cent NH,CO,, or a small proportion of aq. (1.8-3.3 per cent) sufficient to convert 
half the carbamate to carbonate, is heated in pressure vessel at 135-140° and unchanged ma- 
terial removed by distn. The water acts as a catalyst. 


1,285,117—Nov. 19, 1918. 
Harry D. Gress, California, and Courtney Conover, Pennsylvania. (U. S. Govt.) 


Process for the manufacture of phthalic anhydrid, phthalic acid, benzoic 
acid and naphthaquinones, 


NAPHTHALENE is vaporized, mixed with 4 times theoretical amount of air, and passed 
through reaction chamber in contact with oxides of vanadium at temp. of 350-550° (preferably 
500°). Catalyst is distributed on trays and contact with mixed gases aided by baffle plates, 
and slight pressure to cause even flow of gases. One or all of oxidation products result, 
separation being made by fractional sublimation. Pure oxygen can be used, the catalyst may 
be diluted with inert material and other variations of process made. 


1,288,431—Dec. 17, 1918. 
Harry F. Lewis, Illinois, and Harry D. Grpps, California. (U. S. Govt.) 


Process for the manufacture of phenanthraquinone. Phenanthraquinone. 


PHENANTHRENE is melted, mixed with air or oxygen in excess of that required to form 
product, vaporized and vapors heated to 300-550° (preferably 400°) in reaction chamber con- 
taining finely powd. oxides of metals of fifth and sixth periodic groups, preferably V,O;,. 
The metal oxides may also be Mo, W, or U.,, etc., distributed over asbestos, pumice stone, etc. 


1,290,124—Jan. 7, 19109. Charles H. Downs, New Jersey. (Barrett.) 
Dehydration of pyridin. Drying pyridin by one distillation, without NaOH. 


PyRIDIN combines with 3 mols. aq. to a hydrate of constant b. p. 92.5° while benzene-aq. 
mixture (in ratio of 10.325: 1) boils at 69.5°. Moisture content of pyridin having been de- 
termined, sufficient C,H, is added to give above ratio with aq. present, and distillate collected in 
fractions, below 80° (largely aq.), 80-115° (C,H,, residual aq. and a little pyridin) and above 
115° (pyridins). The first fraction is discarded and the second reused in later distn. Modified 
methods are outlined. 


1,291,300—Jan. 14, 19109. Roger N. Watuiacu, New York. 
Manufacture of naphthol and allied products. Naphthols produced with less labor 
and cost. 


Naputuoyt sulfo acid soln. made by usual process is conc. at 100° to saturation and 
added to fused NaOH at 300° in covered vessel, keeping temp. above 280°. 


1,292,019—Jan. 21, 1919. 

Karl NerEsSHEIMER, Carl Boscu, and Alwin Mirrascu, Germany. (Badische.) 
Manufacture of urea. Urea from ammonium carbamate by improved process using cata* 
lyzers. 

Ammonium CARBAMATE ground with 5 per cent K,CO, or other salt of alk. or alk. earth is 
heated in pressure vessel at 135-140°. Ammonium sulfite, 3 per cent, or the chloride, acetate, 
oxalate, selenite, etc., may also be used as catalysts. Products are purified by extraction with 
alc., etc. | 


aS i a 


GROUP XXII.—INTERMEDIATES 359 


1,292,950—Jan. 28, 1919. 
Joseph A. AmBiER, Connecticut, and Harry D. Gisss, California. (U. S. Govt.) 


Process for the manufacture of toluene sulfonic acids. Toluene 4-sulfo or 2.4- 
disulfo acid. 


Sulfuric acid (1.84) at 150° or at 240-250° descending over baffle plates, stones, or other 
obstructions in a tower meets a rising current of TOLUENE vapor. Process is continuous, re- 
quires less acid than. former methods and as product is removed rapidly from reaction vessel, 
contamination with isomers is reduced to a minimum. 


1,293,610—Feb. 4, 1919. Harry F. Lewis, Illinois, and Harry D. Grgss, California, (U. S. 
Govt.) 


Method of purifying commercial anthraquinone. Purifying anthraquinone. 


Commercial ANTHRAQUINONE, 1 part, and 2 parts fine Fe powd. wet with 50 per cent alc., 
is mixed with 30-50 parts hot 20 per cent NaOH and heated to 100° for 15 min., filt., fresh 
alkali added, heated and filt., and operation repeated a third time. Filtrates are cooled and 
ANTHRANOL oxidized by current of air. 


1,295,339—Feb. 25, 19109. Karl P. McE roy, District of Columbia. (Chem. Dev.) 
Process for making chlorhydrins, 


Apparatus similar to fractionating column is shown whereby gaseous OLEFINS (ETHYLENE, 
propylene, butylene, etc.) from cracking of petroleum oils, mixed with Cl gas are forced by 
current of steam upward through the tower against a descending current of aq. near the boiling 
point. HCl is absorbed by the aq. and removed to reservoir at bottom of still. Chlorhydrins 
and steam pass out at top of still which is kept at 95-100° into a condenser and separator. 
Excess aq. and olefin with limited Cl yields more chlorhydrin and less ethylene dichloride 
(Dutch liquid) and vice versa. Detailed uses are given. 


1,297,170—Mar. 11, 1910. Alfred E. Hottey and Owen E. Mort, England. 
Nitration process. Trinitro toluol by continuous process. 


Apparatus is shown in which an organic substance such as nitro TOLUENE is fed in at one 
end of a series of circular pots while 92-94 per cent H,SO, is entered at the other end and 
mixed acid of 90 per cent HNO, is introduced at measured rate into intermediate pots. Each 
pot has two compartments communicating by small hole. In the first the contents are agitated 
and after passing through the hole into the other they are allowed to settle into two layers, 
the organic material on top flowing one way, and the acid at the bottom the opposite way, the 
flow of each liquid being due to difference in head. Pots may be placed level or in cascade 
form and pump may or may not be required. 


1,297,792—Mar. 18, 19109. E. Camus, R. DucueEmin, and G. CriguresorurF, France. 
Preparation of lead acetate. Saponification of ethyl acetate or other esters with lead 
oxide. 


A mixture of ETHYL acetate, water and PbO is heated slightly to start reaction which con- 
tinues without further heating, and may even require cooling. 


1,298,356—Mar. 25, 1919. J. Kortscuet and M. Brunet, France. (Soc. Chim.) 


Production of acetic anhydrid and acetaldehyde. Acetaldehyde and acetic anhyd. 
produced in quantitative yields and separated in one operation. 

ETHYLIDENE diacetate is heated with catalyst at temp. lower than b. p. of the acetate and 
of one of the products, acetic anhyd. Catalyzers are sod. pyrosulfate, meta boric acid, sulf- 
acetic acid, etc., temps. range from 100-140°, and an inactive solvent or diluent of b. p. 200- 
250° may be used. 


1,200,227—Apr. 8, 19109. 
J. A. Amsier, Connecticut, and H. D. Grsss, California. (U. S. Govt.) 


Preeess for the manufacture of aromatic sulfonic acids. 


A continuous counter current process whereby vapors of hydrocarbons rise through a 
tower against a descending stream of H,SO, at temp. above b. p. of hydrocarbon, the un- 
changed hydrocarbon vapors and water formed passing out at top of tower and acid carrying 
the sulfonic acids being removed below. Tower is equipped with baffle plates, pebbles, coarse 
pumice stones, etc. Conditions of temp., strength of acid and duration of heating are varied in 
accorl with material to be treated. A temp. of 111° and acid of sp. gr. 1.84 is employed for 
TOLVENE. 


360 DIGEST OF PATENTS 


1,800,228—Apr. 8, 1919. 
J. A. AmeBier, Connecticut, and H. D. Gisss, California. (U. S. Govt.) 


Process for the manufacture of benzene sulfonic acids. 


Process is similar to that described in 1,300,227 and when applied to BENZENE a temp. of 
150° and acid strength of 1.84 are employed. 


1,801,360—Apr. 22, 1910. Andrew BEenpER, New Jersey. (Beach.) 
Process of sulfonation of aromatic hydrocarbons. 

Apparatus is shown wherein conc. BENZENE sulfo acid is made by a series of alternating 
sulfonation and water elimination steps, the former at atrnospheric pressure, is continued until 


ratio of acid to water is below 78:22, then benzene vapors are charged in under vacuum at 
130-180° to remove water and increase this ratio so that further sulfonation may take place. 


1,801,388—Apr. 22, 1919. 
Courtney Conover, Pennsylvania, and Harry D. Grsss, California (U. S. Govt.) 
Process for the purification of crude phthalic anhydrid. 

Crude PHTHALIC anhyd. is dissolved at 50-70° in CCl, or gasolene, CS,, CHCl, or other 
suitable non-aq. solvent, passed through a filter into vessels containing decol. char, and from 
thence through a series of vessels at descending temps. from 70° to 10° the various crops of 
crystals ranging from pure phthalic anhyd to impurities free of it. Mother liquor is reused. 


1,301,662—Apr. 22, 1919. Robert E. Divine, Ohio. 


Sulfonated-mineral-oil-sludge product and process of making. Alkali earth 
sulfonate of mineral oil for saponifying or detergent purposes. 

Sludge produced from sulfonating mineral o1L is mixed with 1.5-2 parts aq. and let stand 
8-12 hours. Heat is generated, SO, evolved and the free oil that separates is decanted. Under 
layer is neut. with lime, filt. and reddish liquid is salted out. (20 per cent NaCl). Color 
remains in liquid and calcium sulfo acid of mineral oil is separated with yield of 50-60 per 
cent of original sludge. 


1,301,663—Apr. 22, 19109. Robert E. Divine, Ohio. 
Product and process of producing an alkali-metal sulfonate having the 
properties of a detergent. Sodium sulfonate of mineral oil. 

An alkali earth sulfonate of the soluble portion of a sulfonated mineral oil sludge pre- 
pared as in 1,301,662 is treated with an equivalent amount of an alk. salt, such as Na,CO,, 
the alk. earth carbonate filt. out and soln. evapd. to desired consistency. Product is very sol. in 
aq. (less than one vol.) is neut. detergent and will not readily salt out. 


1,801,78S5—Apr. 22, 19109. Charles R. Downs, New Jersey. (Barrett.) 
Sulfonation of hydrocarbons. Sulfonation without neutralization and loss of acid. 


BENZENE or other hydrocarbon, is mono sulfonated by usual process and the second sulfo 
group introduced by removing water from mixture under vacuum of o0.5-1 inch and temp. of 
260-280° or below the point where decompn. of sulfo product would take place, and the dis- 
tillation continued until the water and practically all sulfuric acid has distilled over leaving the 
sulfo product with less than 5 per cent acid, that can be neut. by alk. ready for fusion with- 
out employing lime. Sketch of apparatus is shown. 


1,301,796—Apr. 22, 19109. John M. Weiss, New York. (Barrett.) 
Process of purifying carbazol. 


Com’l CARBAZOLE containing 10-15 per cent impurities (anthracene, etc.) is mixed with 2-6 
parts 90-98 per cent H,SO, at 35°, the acid being added in a thin stream. From 8-12 parts 
aq. are then added and the pptd. 96 per cent unsulfonated carbazol filt. from the soluble sulfo 
acids of the impurities. Sublimation gives pure carbazole. 


1,801,909—Apr. 209, 1919. Fabricius CosELiis, Pennsylvania. 
Manufacture of synthetic carbolic acid. Synthetic phenol with recovery of sulfuric 
acid in form of a valuable by-product. 


Aq. soln. of BENZENE sulfo acid and sulf. acid produced by sulfonation of benzene is 
neut. with ZnO or other zinc comp. to form ZnSO, and zinc salt of the sulfo. acid. The cal- 


GROUP XXII.—INTERMEDIATES 301 


culated quantity of BaS is added to ppt. ZnS and BaSO, (lithopone) and leave barium benzene 
sulfonate in soln. from which it is recovered and fused to form phenol by usual method. 


1,302,011—Apr. 29, 19109. Jens A. CuristiANsEN, Denmark. 
Method of producing methyl alcohol from alkyl formates. 
Mertuyt alcohol and CO, 1 part each, may be combined under pressure to form METHYL 


formate and the latter when treated with H in presence of oxides of copper (more or less re- 
duced) at 180°, and at atmospheric pressure or above, yields 2 parts methyl alcohol. 


1,302,273—Apr. 29, 1919. Alan I. Appresaum, New Jersey. (Import By-) 
Process of manufacturing benzaldehyde. Oxidizing CH te CHO: 

TOLUENE and equal parts finely ground MnO,, together with 1.5 parts dil. sulf. (1:3) acid 
and a catalyst such as ferric, copper or cerium sulfate, equal to 5 per cent of MnO,, are boiled 
in an acid proof vessel and resulting benzaldehyde (b. p. 179°) and unchanged toluol (b. p. 


110°) distilled off by steam, separated from aq. and fractionated at 120°. Drawings and de- 
scription of apparatus given. 


1,303,168—May 6, 1919. 
Courtney Conover, Pennsylvania, and Harry D. Gisss, California. (U. S. Govt.) 
Process for the manufacture of anthraquinone. Anthraquinone. 


Vapors of ANTHRACENE are mixed with air or oxygen in excess of theory and heated to 
250-650°, preferably 500°, in reaction chamber in close contact with oxides of metals of fifth 
or sixth periodic groups, preferably Mo,O,, as fine powder or distributed over porous material. 


1,303,624—May 13, 19109. Charles C. Antum, Pennsylvania. (du Pont.) 
Process of producing anilin hydrochlorid. Anilin HCl as white crysts. by improved 
process. 


Anitin dissolved in 7 parts benzene, or CCl,, solvent naphtha, or other volatile solvent 
is treated with a current of dry HCl gas. The hydrochloride is less soluble and ppts. 


1,303,639—May 13, 1919. Charles R. Downs, New Jersey. (Barrett.) 
Process of treating hydrocarbons. Purifying crude, mixed anthracene, phenanthrene 
and carbazole. 


Crude ANTHRACENE in benzol or other suitable solvent, is treated with ultra violet light in 
absence of oxidizing agent, whereby it is polymerized to para or “di”? anthracene and ppts., 
while CARBAZOLE, PHENANTHRENE and other impurities are unchanged and remain in soln. 
PHENANTHRENE is removed by soln. in solvent naphtha, before or after treatment with ultra 
violet light, and CARBAZOLE can be recovered from residue after removal of other two. 


1,303,779—May 13, 19109. Robert E. Divine, Ohio. (Twitchell.) 
Mineral-oil sulfonic acid and process of making same. Free sulfo acids of min- 
eral oils. 


Process and materials are same as in 1,301,662 but product instead of being converted to 
the Na salt as in 1,301,663, is separated as the free sulfonic acid by adding an equivalent 
amount of an acid, such as H,SO,, which will combine with the alk. earth base to form a ppt. 
that can be removed, leaving free sulfo acid of the mineral oil. 


1,306,221—June to, 1919. Carleton Eunis, New Jersey. (Chadeloid.) 
Composite solvent and process of making same. _ Benzyl chloride mixed with 
benzyl alcohol, etc. 

Vapors of TOLUENE, or similar hydrocarbon, are mixed with 0.5 mol. Cl, and passed in 
continuous stream through tubes heated at 180-200° (or 75-100° above the b. p. of toluene). 
Larger proportions of Cl yield benzalchloride or the trichloride. Part conversion to benzyl 
alcohol and a mixed solvent results when mono chloride is heated at 50 lbs. pressure with dil. 
NaOH containing a little alk. acetate. Halogen can also be introduced in nucleus. Drawings 
and description of apparatus are given. 


1,306,963—June 17, 1919. J. Koetscuet and M. Bruvet, France. (Soc. Chim.) 
Process for the production of acetic anhydrid and polymerized or non- 
polymerized acetic aldehyde or acetie acid. 
ETHYLIDENE diacetate is heated at 70-80° in vacuum (100 mm.) with 2 per cent catalyst 
such as H,SO, (66°). Para ALDEHYDE and acetic anhyd. are formed quantitatively and may be 


362 DIGEST OF PATENTS 


separated as such or the former converted by depolymerizing agents into acetaldehyde. The 
b. p. of ethylidene diacetate under 100 mm. pressure is 115°. 


1,307,570—June 24, 1919. Herbert WINKEL, Delaware. (du Pont.) 
Process of producing dialkyldiarylureas. Di or tetraalkyl diary] urea. 


PHOSGENE is passed into a mixture of mono (40 per cent) and dimethyl aniLIn (50 per 
cent) at temp. of 80-90°. A little anilin (10 per cent) may also be present. The dimethylanilin 
HCl formed acts as a solvent for methylanilin until it enters reaction. Excess amin is dis- 
solved by dil. HCl and pptd. product filt. out. 


1,308,356—July 1, 19109. Arthur E. Hourenan, Delaware. (du Pont.) 
Apparatus for the manufacture of diphenylamin. Apparatus patent only. 


ANILIN, mixed with small quantity of catalyst such as NH,I (1-4 per cent), is heated at 
275-300° in autoclave for 48 hrs., NH, being removed from time to time by opening pressure 
valve in extension pipe which serves as condenser for anilin. Preferably from 0.75-2 per cent 
aq. should be present. Mixed reaction products are fractionated and redistilled and catalysts may 
be recovered. Drawings of apparatus given. 

Note 1,314,538 for product patent. 


1,308,757—July 8, 19109. Alexis C. Houcuton, New York. (Semet-Solvay.) 
Manufacture of phenol. Omitting one step in process for mfr. of phenol. 


Caustic soda 76 per cent, is melted at 300° and about equal parts benzene sulfonation re- 
action mixture containing 85-94 per cent sulfo acid and 13-2 per cent free sulfuric, is added 
in small streams, keeping temp. at 300-350°. Pptn. of sulfonation mixture and separation as 
Ca or Na salts prior to fusion is avoided and apparatus and labor therefore saved. 


1,308,763—July 8, 19109. Jacob M. Monetss, New York. (Chem. Dev.) 
Method of making chlorinated products. 


Unsat. hydrocarbons, OLEFINS, etc., from oil gas that has been passed through a heated 
zone at 700° (50 per cent unsat.) are led into reaction chamber with Cl and steam at 97-100° 
where they meet a counter current of Weldon mud or other form of MnO, as grannular mass 
whereby part of Cl is oxidized and part taken up by the Mn as MnCl,. Olefin chlorides and 
chlorhydrins are formed and their vapors together with unchanged oil gas, steam, etc., are 
condensed and fractionated. Drawings of apparatus are shown. 


1,308,796—July 8, 19109. Karl P. McE roy, District of Columbia. (Chem. Dev.) 
Process of oxidizing hydrocarbons. 


Apparatus is shown by which OLEFIN containing gases are introduced at 4-5 atms. pres- 
sure into the oxidizing liquid containing hypochlorites, permanganates, chromates, peroxides, etc., 
in alk. acid or neut. bath kept by a pump or blower as a foamy mass or emulsion of gas and 
liquid, an excess of ETHYLENE or other olefin being present at all times. Various changes in 
details of method, of oxidizing agents, solvents, activators, temps., agitation, etc., are discussed. 
For chlorhydrin a hypochlorite and CO, as acid to free HOCI are employed. 


1,309,320—July 8, 1919. Carleton Exrtis and A. A. Wetts, New Jersey. (Ellis-Foster.) 
Nitration method. Dinitro chlorbenzene, dinitro phenol and picric acid, etc. 


Sulfuric acid 66° and com’l NaNO, are mixed cold until Cl can no longer be detected in 
vapors, chlor BENZENE is added keeping temp. between 55-70°, then for 6 hours-is held between 
go-100° and for 10 succeeding hours is gradually raised to 125° where it is held for 5 hours. 
Resulting dinitro chlorbenzene is hydrolyzed with boiling 10 per cent NaOH. With PHENOL 
as initial material picric acid and dinitrophenol are produced. ‘The acid sulfate formed in the 
reaction helps to prevent resin formation, and nascent HNO, is better nitrating agent. 


1,309,580—July 8, 1910. John MarsHati, Pennsylvania. (du Pont.) 
Process of preparing dinitrodiphenylamin. Dinitro diphenylamin in fine crysts. 
free of C,H,NH,.HCI and requiring no grinding. 

One part melted dinitro chlor BENZENE is added to 1 part ANILIN at 35-40° and resulting 
liquid poured with stirring into 6 parts aq. at 60°, agitated to form an emulsion, live steam 
introduced to raise temp. to 80° when reaction begins. Red needles of dinitro diphenylamin, 
readily separable from anilin HCl by filtration, washing, etc., result. 


GROUP XXII.—INTERMEDIATES 363 


1,309,683—July 15, 19109. Marston IL. Hamuin, New Jersey. (Amer. Syn.) 


Recovering benzene monosulfonic acid and producing phenol. Using mag- 
nesium salts in phenol production. 


BENZENE sulfo acid sulfonation mixture is neut. and pptd. by MgCO, (Magnesite) aided by 
heat, then cooled and filt. granular ppt. fused directly in NaOH by usual process. The amount 
of Mg salt to be added should be determined by experiment, an excess causing more complete 
pptn. 


1,311,090—July 22, 1919. Lester A. Pratr and Francis N. Brinx, Massachusetts. (Merrimac.) 


Manufacture of naphthalene trisulfonie acid. Naphthalene 1.3.6-trisulfo made with 
minimum amount of H,SO, and increased yield. 


NAPHTHALENE with equal parts 100 per cent H,SO, is heated at 160° for 8 hours to form 
beta mono sulfo acid, mixture cooled, fuming acid (60 per cent SO,) slowly run in and temp. 
raised to 160-180° for 4 hours to form trisulfo comp. Oleum is used in second stage because 
- ready formed beta sulfo acid is not so sensitive to SO, as naphthalene. Residual acid has concn. 
of 100 per cent. 


1,311,158—July 29, 19019. Leon S. Fincu, New Jersey. (Hercules.) 
Process of concentrating acetic anhydrid. Acetic anhydride concentrated to 90.6 
per cent strength. 


AcETiIc anhyd. (69.3 per cent) is added to 0.5 parts anhyd. sod. acetate (67 per cent pure) 
by being blown or sucked into the steam jacketed still used as container, heated under partial 
vacuum, keeping temp. to minimum for distilling acetic anhyd. (70o—-100°) until all of the latter 
has passed over, then temp. raised (g0-170°) to distil acetic acid, which retains 6.1 per cent 
anhydride and leaves some acid in residue of sod. acetate. Recovery efficiency is 97.6 per cent. 


1,311,824—July 29, 1910. Theodore LICHTENHAHN, Switzerland. (Lonza.) 
Process for the manufacttre of ethyl alcohol from acetaldehyde. 


ACETALDEHYDE and hydrogen are combined in presence of a catalyst such as metallic nickel 
at 90-180°. Excess hydrogen, at least 6 times theory, is used in order to remove heat of re- 
action (300 cals. per kilo of alc.) and maintain favorable temp. in reaction chamber. Gases 
are chilled to remove alcohol and hydrogen is recovered and recirculated through apparatus. 


1,311,848—July 29, 1919. Pierre Lerrrs, France. 
Process of separating metaxylene from xylene substances. Selective sulfona- 
tion of xylene isomers. 


Com’l. xyLENE is sulfonated at 50° by 75 per cent H,SO, in presence of 3-xYLENE sulfo acid 
as catalyzer. At this temp. the acid attacks only the meta isomer. After standing the un- 
changed xylenes separate as top layer, and meta sulfo deriv. with excess acid in lower layers 
is removed and desulfonated. 


1,312,127—Aug. 5, 19109. Ralph H. McKeer, New Jersey. 
Process of making phenol. Phenols by more economical process. 

The usual process for making a PHENOL or hydroxy comp. is followed, CaSO, as well 
as CaCO, is used to neut. the sulfonation mixture and evolved gases are collected. Separated 
sludge after forming the phenol from its Na salt is distilled with steam to recover waste 
phenol that would otherwise be lost; sod. sulfite is recovered, 60 per cent being converted to 
caustic; sod. carbonate is also recovered as caustic and other economies accomplished. 


1,314,138—Aug. 26, 1919. Nathan GoopMANn and Benjamin GruspmMan, New York. 
Process of making resorcinol. Resorcinol mfr. with less consumption of ether. 

BEnzEnE is disulfonated, separated as Na salt and fused in NaOH to form the dioxy deriv., 
by usual process. ‘The free resorcinol after making soln. acid is extracted by mixture of ether 
with benzene (proportions not disclosed). Mixed solvent is cheaper, is quite as effective, loss 
by evaporation is less, and last traces of solvent are more readily removed from resorcinol 
residue. 


1,314,538—Sept. 2, 1919. Homer Rocers, Delaware. (du Pont.) 
Method for production of diphenylamine. | 
Process and operation are the same as in 1,308,356 which claims apparatus only. The 
catalyst in current patent is NH,Br (1 per cent of anilin used), and from o0.75-2 per cent 
water must be present. Drawings of apparatus are given. 
24 


364 DIGEST OF PATENTS 


1,314,920—Sept. 2, 1919. Chester ANDREWS, Pennsylvania. (Selden.) 
Process of treating cymene._ 1-Methyl 2-nitro 4-isopropyl benzene, or nitro cymene and 
derived amino comp. 

Spruce TURPENTINE when treated with sufficient CaO to combine with aq. SO, and SO, 
present, filt. or decanted, yields an oil containing 75 per cent cymene and the rest terpenes. 
This oil as such or the fraction boiling at 175° is dissolved in equal parts 98 per cent H,SO, 
or 1.5 parts glac. acetic acid, etc., and 2.3 parts mixed acids (H,SO,: HNO, = 2:1) added at 0°. 
Separated oil may be reduced by Fe and HCl or H and nickel or other catalyst and amino cymene 
distilled with steam. 


1,314,923—Sept. 2, 1919. Chester AnprREWs, Pennsylvania. (Selden.) 
1-Methyl 2-amino 4-isopropyl 5-nitrobenzene. 

Amino CYMENE produced as in 1,314,920 is acetylated in 1.5-2 mols. glac. acetic by re- 
fluxing 15-20 hours, separated products dissolved in 4.5 parts 98 per cent H,SO, at o° and 1.2 
parts mixed acid added. Products may be reduced and then hydrolyzed or may be hydrolyzed 
only and retained as nitro deriv. Substituents in amino group are also claimed. 


1,314,924—Sept. 2, 1919. Chester E. Anprews, Pennsylvania. (Selden.) 
Dimethyl-diisopropyl-benzidin and process of making same. 


1-Methyl 2- or 3-nitro 4-isopropyl BENZENE, (nitro CYMENE), crude or refined, with equal 
parts 70 per cent alcohol and 3.5 parts 30 per cent NaOH are mixed at usual temp. then re- 
fluxed while Zn dust is slowly added. Dimethyl diisopropyl hydrazo benzene or hydrazo cymene 
that results may be: purified as the HCl salt or not, is boiled in 4-5.5 parts aq. and HCl slowly 
added so long as it is absorbed. ‘Transformation to benzidin is then complete and sulfate salt 
is pptd. by H,SO,. . 


Note 1,314,920 and 23. 


1,314,925—Sept. 2, 1919. Chester E. Anprews, Pennsylvania. (Selden.) 
Dimethyl-diisopropyl-benzidin azo dyestuffs and process of making same. 
Diisopropyl tolidin (dimethyl diisopropyl benzidin.) 


Nitro CYMENE is reduced in alk. soln. with Zn to hydrazo cymene and subjected to benzidin 
reaction. 


1,314,927—Sept. 2, 19109. Chester E. AnprEws, Pennsylvania. (Selden.) 


Methyl-amino-isopropyl-benzene-sulfonie acid and process of making same. 
1-Methyl 2-amino 4-isopropyl benzene 5-sulfo acid. 


Amino CYMENE, prepared as in 1,314,920, is heated at 205° in 0.85 per cent parts 98 per 
cent H,SO, or equiv. of fuming acid, for ro hours. 


1,315,229—Sept. 9, 1919. Karl P. McE roy, District of Columbia. (Chem. Dey.) 
Producing chlorhydrins from olefins. 


Apparatus is described whereby OLEFINS are caused to react with a reducible chloride, 
preferably CuCl, at 1oo-160°, the chloride being regenerated with HCl and oxygen (air and 
steam). Process is practically continuous. 


1,315,619—Sept. 9, 1919. Jean Autwece, France. (Soc. Chim.) 
Process for the preparation of primary alcohols. Phenyl ethyl alcohol and homo- 
logs, etc. 


Dry ETHYLENE oxide is passed at 0° into ether soln. of equimol. PHENYL bromide of Mg., 
dry benzene added, ether evapd., dil. H,SO, added to hydrolyze, resulting phenyl ethyl alcohol 
decanted and rectified (b. p. 89° at 4 mm pressure). Homologs and derivs. are claimed. 


1,316,781—Sept. 23, 1919. Hermann Fritzscuet, Switzerland. (Basle.) 
Azo dyestuffs dyeing mordanted goods. 2-Amino phenol 4-sulfanilid, HCl salt, or 
derivs. 


ANILIN, or deriv., is condensed in HCl soln. at 60° with 2-nitro chlor BENZENE sulfo 
chloride, soln. neut. by chalk, separated oil saponified by NaOH and reduced by Na,S, then 
converted to HCl salt. Preparation of the corresponding para amino anilid is described. 


lt oa 


GROUP XXII.—INTERMEDIATES 365 


1,316,823—Sept. 23, 1919. 
J. A. AMBLER, Connecticut, H. A. Luss, Georgia, and H. D. Gisss, California, (U. S. Govt.) 
Process for the manufacture of cymene sulfonic acids. Sulfonation of cymene 
with less consumption of acid. 


Process and apparatus are same as in 1,292,950 using H,SO, (1.84) and temp. 180-190° 
with 4-CYMENE as material. The cymene 2-sulfo acid existing as impurity in the product is 
separated as Ba salt by fractional deposition from conc. soln. Other temps. and conc. of acid 
are claimed : 


1,318,212—Oct. 7, 1919. Henri Leroux, France. 
Process for the production of high-percentage carbazole. 


Pyripin residue from purification of crude anthracene is dissolved in 5 parts hot crude 
cresols (xylenols or phenols) cooled, and crystals of (80 per cent) carbazole separated. A 
second treatment with same solvent yields 90 per cent carbazole. 


1,318,631—Oct. 14, 1919. 
John M. Weiss, New York, and Charles R. Downs, New Jersey. (Barrett.) 
Production of quinone. 


Mixture of BENZENE vapor and air or oxygen is passed at temp. of 300-700° thru tube 
containing a catalyzer such as vanadium oxide (or Mo, W, Au, Ru, Co, Cu, Mn, Pb, Cr, Sb, Ca, 
and Th oxides) on pumice as distributing agent. By varying speed at which mixture is passed, 
the dimensions of tube, the pressure from partial vacuum to far above atmospheric, the fineness 
of the pumice, the temp., the proportions of mixture and of diluent gases such as nitrogen used 
for blanketing effect on oxidation, the relative proportions of quinone and maleic acid, or 
formaldehyde and CO, in product can be controlled. 


1,320,443—Nov. 4, 1919. Elmer K. Bouton, Delaware. (du Pont.) 
Process of diazotization. Diazotizing with niter cake as acid agent. 


ANILIN is converted to sulfate by equiv. amount of niter cake (NaHSO,) showing 35 per 
cent acidity, then NaNO, added in sufficient quantity to react with one-half the anilin. The 
diazo anilin that forms couples with excess anilin to diazo amino benzene, which separates. 
Other amins may be diazotized in similar manner. 


1,320,454—Nov. 4, 1919. Louis M. Dennis, New York. 
Manufacture of hydroxy compounds of aromatic hydrocarbons. 


BENZENE is sulfonated preferably with fuming acid and separated BENZENE sulfo neut. 
with Na,CO,, fused with solid NaOH, melt dissolved in aq. and CO, passed in to separate 
phenol. Carbonate liquors are evapd. until after cooling Na,CO, substantially free from sulfates 
and sulfites separates out and is re-used. 

Note 1,211,923 and 1,212,612. 


1,321,271—WNov. 11, 19109. E. H. Zotuincer and H. Rogruriine, Germany. 
Process for the preparation of aromatic phenols’and their substitution 
products. by 
2-Chlor PHENOL or other saponifiable halogen comp. which contains besides hydroxyl such 
other groups as sulfo, carbo, aldehyde, etc., is heated in an autoclave at 250—260° with 20-25 per 
cent NaOH and a small amount of copper salt, an iodide, iodic acid, V, Ti, Mo, rare earth or 
salts thereof, as catalyst. 


1,321,959—Nov. 18, 1919. 
John M. Wetss, New York, and Charles R. Downs, New Jersey. (Barrett.) 
Production of benzaldehyde. Benzaldehyde from toluene in vapor phase. 


Process and apparatus are similar to 1,318,631, using TOLUENE vapors and equal parts air 
as material, MoO, as catalyst, and a temp. of 500° at atmos. pressure. Process is subject to 
wide variations as indicated in previous patent without forming by products such as H,O and 
CO, in excessive amounts. Very little complete combustion accompanies the reaction. 


1,321,994—Nov. 18, 1919. Charles R. Downs, New Jersey. (Barrett.) 


Sulfonation of hydrocarbons with SO,. 


BENZENE, NAPHTHALENE or other hydrocarbon is mixed in vapor phase with SO, from 
contact chambers and passed through vessels or tubes heated to 90-180° or any suitable temp. 


366 DIGEST OF PATENTS 


Temp. pressure and time of reaction, dilution of SO,, the hydrocarbon employed and other 
factors affect the rapidity and degree of sulfonation and position of sulfo group. 


1,322,054—Nov. 18, 1919. Eloi Ricarp, France. 
Manufacture of furfurol. Furfurol mfr. with higher yield and purer and more stable 
products. 


Apparatus is drawn and described in which cellulosic material such as kapok is boiled 
with dil. acid (13-14 per cent HCl) resulting furfurol rapidly distilled off and fractionated into 
furfurol vapor passing on and acid liquid passing back to further react with cellulose material, 
furfurol being finally distilled in vacuum at low temp. (90-92°). 


1,322,580—Nov. 25, 19109. ’ Frederick T. Kitcuen, New York. (K. & T. Chem.) 
Method and apparatus for producing quinone and quinol. 


Apparatus is shown wherein BENZENE may be oxidized below 12° to quinone by an electric 
current of not more than 0.5 amp. per sq. dcm. in an electrolyte of greater specific gravity so 
that the benzene as it rises through the electrolyte meets oxygen at the instant it is liberated near 
the anode by the current. An excess of benzene serves as solvent for quinone as it forms. 
Apparatus and method for reducing quinone to QguINOL are also given. Process is continuous and 
recurrent. 


1,322,983—Nov. 25, 1910. 
John M. Wetss, New York, and Charles R. Downs, New Jersey. (Barrett.) 
Production of diphenyl. Manufacture of diphenyl without loss of benzene by pyrogenic 
decomp. 

BENZENE vapors, 23 vols., mixed with 27 vols. steam, are passed into a reaction chamber 
containing pumice or other distributing agent maintained at temp. of 600—-800° (preferably 700°) 
and 60 lbs. pressure. Proportions of mixed vapors, the kind of distributing substance, the temp., 
the pressure, the form of apparatus, etc., may be varied. 


1,324,143—Dec. 9, 1919. Benjamin T. Brooxs, Pennsylvania. (du Pont.) 
Manufacture of toluene. ‘Toluene manufacture by cracking of xylenes. 


Crude solvent naphtha, containing 7o-8o0 per cent mixed xylenes, freed from aq., is re- 
fluxed with 5 per cent AICI, in an apparatus so constructed that vapors are cooled to 105-115° 
at which temp. resulting toluene distils over and unchanged xylenes return to reaction vessel. 
Condensate is about 0.67 toluene, 0.17 benzene and remainder is heavy oils carried over mechan- 
ically. Benzene and xylenes are reused. Process is continuous and AICI, is renewed at intervals. 


1,324,443—Dec. 9, 1919. Re. 15,520—Jan. 9, 1923. 
Courtney Conover, Pennsylvania. (Selden.) 
Apparatus for bringing about and controlling reactions between gases. 


Apparatus consists of multiple reaction chambers, to contain a catalytic material, with 
separate compartments above and below each chamber to contain a cooling liquid medium that 
boils at reaction temp., means for transferring heat of cooling vapors to incoming gases, means 
for supplying and distributing reaction vapors to catalytic chambers, etc. . 


1,324,715—Dec. 9, 19109. Chester E. AnprEwS, Pennsylvania. (Selden.) 
Process of oxidation of aromatic bodies. 


ANTHRACENE, XYLENE, or other aromatic hydrocarbon is oxidized to ANTHRAQUINONE, — 
PHTHALIC ANHYD, etc., by boiling with H,SO,, preferably 50 per cent, containing an oxidizing — 
agent such as Na,Cr,O,, CrO or MnO,, and a catalyst such as V,O, or Mo,O,, which are still 
more efficient when mixed with oxides of metals of the fifth or sixth periodic groups. F 
1,324,716—Dec. 9, 19109. Chester E. Anprews, Pennsylvania. (Selden.) © 
Process of purification of crude anthraquinon. Separation of anthraquinone in ; 

crude product from phenanthrene, phenanthraquinone, anthracene, methyl anthracene, methyl — 

anthraquinone, etc. 


carried by blast of suitable gas into and through a receiver of 6 compartments of successively in- 

creasing height, separated by screens of wire gauze, provided with delivery doors, shakers, 

outside cooling jets, and a pipe to return gas to vaporizing chamber. Fractional condensation — 

of various ingredients results. Apparatus described and drawing given. 
Note 1,324,717 and 1,336,182. 


7 
. 
Crude ANTHRAQUINONE vaporized at 300° in one vessel which may contain baffles and — 
zi 
x 


GROUP XXII.—INTERMEDIATES 367 


1,824,717—Dec. 9, 1919. Chester F. Anprews, Pennsylvania. (Selden.) 
Treatment of anthracene press-cake. Recovery of anthracene, carbazole, etc. 


Crude anthracene press cake, containing 60-70 per cent impurities, largely phenanthrene, 
methyl anthracene, and carbazol, is heated to 1oo° with 80-85 per cent caustic to convert 
CARBAZOLE into its Na salt and mass then heated to 200-250° with current of inert gas in 
apparatus described in 1,324,716, which fractionates anthracene, methyl-anthracene, phenanthrene, 
etc., while the Na carbazole salt remaining in vessel may be purified and pptd. by acid from aq. 
soln. 


1,325,841—Dec. 23, 1910. Hermann Fritzscuet, Switzerland. (Basle.) 


Azodyestufis dyeing mordanted goods. 2-Amino phenol 4-sulfamid, the imid or other 
amids or imids of amino ortho-oxy aryl sulfo acids. 
2-Nitro chlor BENZENE 4-sulfo chloride in 20 per cent NH, soln. is evaporated to dryness 
at 100°, dissolved in aq., neut. and pptd. with HCl, boiled in NaOH to replace Cl with OH, 
reduced with Na,S in neut. soln., excess Na,S removed and pptd. by salt. To produce the 
imid, equimols. of amid and of the original sulfo chloride mixed with sod. acetate are heated 
together, dissolved in aq., and the 2.2’-dinitro DICHLORBENZENE 4.4’-disulfonimid salted out. 


1,326,040—Dec. 23,. 1919. Thomas H. Durrans, England. (Roberts.) 
Manufacture of organic-acid anhydrids and chlorids. 

A current of mixed SO, and Cl gases is introduced into a closed vessel containing anhya. 
alk. acetate mixed with 1 per cent ethyl acetate as catalyst, preferably with cooling. Proportion 
of Ci can be varied to produce anhydride or acetyl chloride. Similarly phenyl acetic anhydride 
can be produced from sod. phenyl acetate, butyric anhydride from sod. butyrate, benzoyl 
chloride from sod. benzoate, etc. Catalysts may be esters, purely organic or organic salts of 
inorganic acids, organic oxides, hydrocarbons, aldehydes, phenols, acetal or tricresyl phosphate 
ELC, 


1,326,045—Dec. 23, 19109. Sigurd Griertsen, Norway. 
Process of converting cyanamid into urea and ammonium compounds. 

Crude cYyANAMID or aq. soln. is heated with aq. SO, in autoclave at 90° with catalyzer it 
desired. Product can be dried and used as fertilizer or UREA separated. Graphite can be re- 
covered from the insol. residue, calcium sulfite from soln. by neutn. with CaO or driving off 
SO, and ammonium sulfite conserved as free NH, or oxidized to sulfate. 


1,826,515—Dec. 30, 1919. Pierre Leroux, France. (Soc. d’Eclair.) 
Production of pure anthracene. Purifying anthracene. 
Crude ANTHRACENE, 18-25 per cent, is dissolved in warm phenol, cresol, (mixture ot 


o, m and p), or homolog, cooled to crystn, filt. or centrifuged, washed, etc. A 50-60 per cent 
anthracene results and a second treatment or extraction with pyridin still further concentrates 


the product. 


1,330,074—Feb. 10, 1920. Richard Hryprr, New York. (Williamsburg.) 
Method of nitrating chlorbenzol. Dinitro chlorbenzene mfr. with minimum danger 
and loss. 

Chlor BENZENE is added to 7 parts 66°H,SO, containing the theoretical amount of NaNO, 
to produce dinitro deriv. while temp. is kept between 25-65°. Chlor benzene is added at the 
rate at which it is used up in the reaction. Mixture is then heated to 95°, heat turned off, and 
after temp. has risen spontaneously about 10-15° further heat is applied and nitration com- 
pleted at 115-120.° Process requires 8-8.5 hrs. Method for mfr. of Sulfur Black is described, 
not claimed. 


1,330,624—Feb. 10, 1920. Robert E. Diving, Ohio. (Twitchell.) 
Process of recovering sulfonic acids from mineral-oil sludge. Improved pro- 
cess for 1,301,662, etc. 
Process is similar to preceding patents except that in salting out the alk. earth sulfo acid 
of the mineral oil, a sol. salt of the same alk. earth is used alone or together with NaCl. 
The salting out is more complete and formation of sol. Na salt is decreased as concentration of 


alk. earth ions is increased. 


368 DIGEST OF PATENTS 


1,332,028—Feb. 24, 1920. V. Costentz and H. W. Waker. New York. (Com. Research.) 
Side-chain oxidation. Benzoic acid, etc., from toluene. 


TOLUENE, or other side-chain aromatic deriv., is treated with 40 per cent HNO, at 90° in 
reflux apparatus, the hydrocarbon resting in a layer above the acid. Cu, Zn, starch, FORMALEHYDE 
or preferably para formaldehyde is added to initiate a reduction of the HNO,, and resulting 
vapors of nitrogen oxides react while passing thru the toluene, are reoxidized in the air above 
and return to reaction zone for further work or may be conducted into another vessel in 
series. 


1,332,203—Mar. 2, 10920. Louis M. Dennis, New York. 
Method of sulfonation of hydrocarbons of the aromatic series. Naphthalene 
2-sulfo. 


NAPHTHALENE is heated at 160° with 75 per cent H,SO, for 1-2 hours, and cooled product 
extracted with toluene which when cooled to 27° deposits sulfo acid free from alfa deriv. 
Note 1,228,414. 


1,333,694—Mar. 16, 1920. Nils L. AkrerBLom, Sweden. 
Method of recovering cymene obtained in sulfite-cellulose process. 


Apparatus is described and drawn whereby the CYMENE produced in sulfite cellulose mfr. 
may be topped off into specially constructed vessels in which the cymene is forced by means of a 
liquid of greater sp. gr. into relatively narrow portion of the receptacle and collected in nearly 
pure condition. 


1,334,033—Mar. 16, 1920. Arthur E. HouteuHan, Delaware. (du Pont.) 


Process for the manufacture of lower-boiling hydrocarbons from higher- 
boiling hydrocarbons. ‘Toluenes from xylenes, etc. 


Process is essentially the same in 1,324,143, a preliminary distillation of crude xyLENES being 
made to obtain a material of b.p. 135-145°, containing less high boiling oils and consisting 
principally of meta xylene. The amount of catalyst may vary from 5-20 per cent and it is 
claimed that either in the cold or on slight warming AICI,, unites with part of the hydrocarbon 
to form the active catalyst, a red liquid of undefined composition. 


1,336,182—Apr. 6, 1920. Chester E. Anprews, Pennsylvania. (Selden.) 
Phthalic anhydrid. 


Apparatus is shown and described in which mixture of NAPHTHALENE vapor and air at 
temp. of 350-550° (preferably 450°) is forced over or thru a catalyst such as molybdenum 
oxide and products of reaction consisting of phthalic anhydrid, phthalic acid, 1.4-napthoquinone, 
benzoic acid, aq. and unchanged naphthalene are fractionally condensed in a series of chambers 
of successively increasing size and height separated by screens thru which the vapors pass, temp. 
in each chamber being controlled by spray nozzles that distribute water over the outside of 
chamber. Crystals as they accumulate on the screens are dislodged by weights that strike 
screens periodically. 


1,337,317—Apr. 20, 1920. Arthur E. HourtHan, Delaware. (du Pont.) 
Process for the production of lower-boiling hydrocarbons from higher- 
boiling hydrocarbons. Toluene from xylenes. 


Process as described in 1,334,033 is improved by use of vacuum whereby a greater yield 
of toluene is obtained and plugging of condensers with AICI, is reduced. Pressure of 14 inches 
and temp. of 100-116° are effective. 


1,338,363—Apr. 27, 1920. Max Fiscuer, Switzerland. (Geigy.) 
Process of making 2-aminoanthraquinone. 2-Amino anthraquinone in higher yield. 
Sodium salt of ANTHRAQUINONE 2-sulfo acid is heated at 205° in autoclave with 10 parts 
conc. aq. (23 per cent) NH, containing 0.6 part CaCl, and 1 part MgCl,, mass cooled, boiled 
out with dil. HCl and dil. soda. Yield is 79.2 per cent of theory. NH,Cl may replace part of 
MgCl,. 
Note 1,338,364 and 1,340,603. 


1,338,364—Apr. 27, 1920. Max Fiscuer, Switzerland. (Geigy.) 


Process of making 2-aminoanthraquinone. 2-Amino anthraquinone in increased 
yield. 


~~ ae 


GROUP XXII.—INTERMEDIATES 369 


Same process as in 1,338,365, using ANTHRAQUINONE 2-sulfo acid, except that NH,Cl is 
used in place of MgCl,. Yield is 69.5 per cent of theory. 


1,338,979—May 4, 1920. Henry Dreyrus, England. 
Manufacture of acetic anhydrid. Acetic anhydride by treatment of sodium acetate 
with SO,. 


Process is similar to 1,283,115 in which dry acetate of Na or Ca mixed with liquid acetic 
anhyd. is acted upon by SO,. Temps. of 0° to 20° cause SO, to solidify while at higher 
temps. it decomp. the anhyd. Patent claims dilution of SO, with indifferent gases so that 
mixture can be cooled to required temp. without becoming solid. The contact process is an 
important source of SO,. 


1,339,310—May 4, 1920. Ernst Wirtu, Germany. (Chem. Found.) 
Producing resinous bases from tar. High boiling point tar bases of series C,,H,N, 
etc., from tar, tar oils, or pitch. 
Tar, freed of benzene, homologs, phenol and pyridin, is diluted with o.5 parts coal-tar oil if 
too viscid, separated carbon filt. out, washed first with o.1 parts NaOH (1.15), alk. soln. of 


phenols removed, then with 0.1 parts H,SO,(1.12), residue extracted with boiling aq. to remove 
sulfates of bases, soln. made alk. with NaOH, and bases distilled over in vacuum, quinolin, and 


homologs coming over at 236—-290° and new bases with acridin at higher temps. 


1,340,603—May 18, 1920. Max Fiscuer, Switzerland. (Geigy.) 
Process of making 2-aminoanthraquinone. 2-Amino anthraquinone. 


Same process as 1,338,363 and 1,338,364, using ANTHRAQUINONE 2-sulfo acid, except that 
NaCl is used instead of MgCl,, or of NH,Cl, or a mixture of all three may serve. Yield is 
70 per cent of theory. 


1,344,673—June 20, 1920. Carl Boscu, Germany. (Chem. Found.) 
Manufacture of urea and of intermediate products. Ammonium carbamate and 
urea. 


Gaseous or liquid NH, and equimol CO, are heated at 100-110° and pressure of 3 atms. 
or more in lead or silver lined autoclave that will withstand high pressure, cooled and separated 
as ammonium carbamate or further heated at 130-140° and 30-50 atms. until converted to 
urea. (NH,),CO, is also formed. 


1,345,373—July 6, 1920. Lucas P. Kyripes, New York. (Gen. Chem.) 


Process of producing halogenated homologues of benzene. MHalogenation in 
side chain of aromatic hydrocarbons. 

Dry TOLUENE is heated to 90° in reflux apparatus with 2 per cent sulfur chloride and 0.5 
parts Cl gas introduced. Addition of 2 per cent acetyl chloride improves yield and quality of 
benzyl chloride. When temp. range is 100-180° and Cl passed until liquid reaches sp. gr. 
1.272 the product is benzal chloride and when sp. gr. is 1.315 about 0.67 of liquid consists of 
benzo trichloride. Instead of sulfur chloride in each case an equivalent amount of ground 
sulfur may be used. Other side chain hydrocarbons are claimed. 


1,345,589—July 6, 1920. Carleton E.iis, New Jersey. 
Process of hydrogenation. Hydrogenating oils, fats, etc. 

Apparatus shown in 1,217,118 and in drawing attached consists of towers that are packed 
with granular material such as charcoal, which may carry a catalyzer, and towers may also be 
lined with such catalyzer. Fatty oils, fatty acids or glycerides, resins, etc., containing a colloidal 
catalyst, (Ni, Co, Fe, etc.) at temp. of 150-200° flow downward thru the tower and meet a 
rising current of hydrogen under pressure of 10-25 lbs. Solvents may be employed. 


1,348,722—Aug. 3, 1920. William Kirsy, England. (South Met. Gas.) 
Purification of carbazole. 

Crude cARBAZOLE 1s dissolved in 19 parts conc. H,SO, at usual temp. and exposed to moist 
air or to current of moist air suitably controlled. After 24 hours about 94 per cent of carbazole 


separates as crystals that may be easily filt. out. The amount of water necessary may be intro- 
duced in various other ways. 


370 DIGEST OF PATENTS 


1,351,888—Sept. 7, 1920. Axel V. Brom, Switzerland. 
Method for producing asymmetric carbamids. (Product also claimed.) Asym- 

metric carbamids produced with high yield and purity. 

2-AMINO 5-NAPHTOL 7-sulfo in alk. soln. and 3-TOLUYLENE diamin or other, with two primary 
amino groups reacting with different velocities, together with PHOSGENE are run simultaneously 
in molecular amounts into a vat at temp. of 40°, in presence of sufficient alkali to neut. HCl 
split off. One amino group of diamin may be replaced by an acid radical such as formyl, or 
protected by a substituent in ortho position. 


1,355,098—Oct. 5, 1920. 
John M. Wetss, New York, and C. R. Downs, New Jersey. (Barrett.) 
Catalytic oxidation of anthracene. Anthraquinone. 
Mixed ANTHRACENE vapor and air or oxygen are passed at 300-500° thru tubes containing 
VO, or other catalyzer, distributed on pumice or other granular or fibrous materials. Pressures 


may vary from less than 1 atms. to 2 atms. and presence of diluent gas with oxygen regulates 
reaction. 


1,3855,100—Oct. 5, 1920. k 
J. M. Weiss, G. C. Bartey and R. S. Porter, United States. (Barrett.) 
Production of chlorbenzoyl benzoic acid. Chlor benzoyl benzoic acid in higher yields. 
PHTHALIC anhyd. finely ground, mixed with 1.8 parts coarse freshly sublimed AICI, is 
gradually added to 10 parts chlorbenzene at 118-123° (about 120°), HCl given off may be 
recovered. Mixture is diluted with ice, pptd. by 60 per cent H,SO,, excess chlorbenzene distilled 
off, soln. filt. and crude chlor benzoyl benzoic acid dried, washed, etc. Improvements consist 
in fine grinding of phthalic anhyd. and AICI,, the fresh condition of latter, the regulation of 

temp. of reaction, and method of recovery of product. 


1,357,467—Nov. 2, 1920. Kenneth P. Monrot, District of Columbia. 
Method for the manufacture of furfural and volatile organic acids from 
extracted corncob pentosan. 


Extracted corn cob PENTOSAN as described in 1,285,247, is boiled with 1.5 parts 35 per cent 
H,SO, and furfural with volatile organic acids resulting from reaction is distilled off with 
Steam and fractionated. Or distillate is neut. with Na,CO,, saturated with NaCl and extracted 
with ether. 


1,358,324—Nov. 9, 1920. Tom §S. Moors, England. 
Reduction of substituted nitro compounds, nitroso and azo compounds, or 
the like. 4-Amino phenol, 2-phenylene diamin, etc. 


Aromatic nitro, nitroso or azo comps. are reduced with cast iron in relatively coarse 
particles and aq. soln. of a chloride such as CaCl, or NaCl. Yields are high. 


1,859,071—Nov. 16, 1920. Frederick J. Kaurmann, West Virginia. (Ritchie.) 
Process of making fatty-acid halids and phosphorus oxyhalids. Chloracetic 
and other halogen organic acids. 
Glac. aceTIc acid and equimol. PCl, are mixed below reaction temp., preferably at 10°, and 
1 mol. dry cold Cl gas introduced at this temp., then products fractionally distilled, acetyl 
chloride having a b.p. 51° and POCI,, b.p. 106.5°. 


1,364,547—Jan. 4, 1921. C. R. Downs and R. S. Potrrrer, New Jersey. (Barrett.) 
Separation of meta and para cresols. Cresols separated by selective sulfonation with 
SO,. 


Gaseous SO,, either pure or admixed with unreactive gases, is passed into crude CRESOL at 
15—s50° and selectively sulfonates the meta isomer without forming H,O. 4-Cresol is distilled off 
with steam under reduced pressure, vacuum released and 3-cresol sulfo decomposed and dis- 
tilled with steam at 120° before or after crystg. from soln. by cooling, or solvents may be 
applied instead of steam distn. 


1,365,024—Jan. 11, 1921. Lloyd C. Daniets, New York. (National.) 


Method of purifying benzanthrone. Purifying benzanthrone. 


Crude BENZANTHRONE is boiled (130°) in 6 parts chlorbenzene in a special apparatus 
claimed in another patent, removed from vessel, cooled to cryst. and filt. Product has m.p 


ee a te 


GROUP XXII.—INTERMEDIATES ye! 


166-170°. Further extraction will remove more impurities and raise m.p. to 174.4°. Other 
halogen derivs. of aromatic hydrocarbons may serve as solvents but alc., acetone, acetic acid, 
toluol, xylol, etc., are not suitable. Solvent may be recovered. 


1,365,046—Jan. 11, 1921. Carleton Extis, New Jersey. (Hunt.) 
Separation process of making alcohols. 


OLEFIN material produced from cracked gasolene is mixed gradually with equal parts 
H,SO, (1.8), resulting sulfate is hydrolyzed by adding 0.2 parts aq., about 0.1 parts benzene or 
other material having solvent affinity for alcohol is then added and mixture centrifuged. Use 
of benzene or similar solvent causes a complete separation of products into layers. 


1,365,407—Jan. 11, 1921. _ Walter J. Hunn, California. 
Production of phenols from redwood. (Product also claimed.) 


Comminuted resinous redwood is destructively distilled above 450°, tar collected and 
fractionated at 150-250°, distillate extracted with caustic alk. and phenols separated from alk. 
soln. with acid. Details of composition of redwood tar distillates and graphic drawing of steps 
in process are shown. 


1,365,849—Jan. 18, 1921. Alexander S. Ramace, Michigan. (Bostaph.) 
Process of producing aromatic hydrocarbons. Toluene from xylenes. 


Solvent naphtha is supplied at rate of 1 gal. per hour at one end of 20 ft. iron tube con- 
taining freshly prepared catalyst consisting of powd. lower oxides of iron or nickel held at 
about 7oo°. Vapor is drawn by reduced pressure from upper to lower part of slanted tube 
against a current of H in excess of amount required, or about 0.25 lb. per hour. About 25 
per cent yield of mixed benzene and toluene is obtained, nearly two-thirds of which is TOLUENE. 


1,365,956—Jan. 18, 1921. Jean B. SEenpERENS, France. (Poulenc.) 
Production of benzoie acid. Selective oxidation of toluene to benzoic acid. 


ToLUENE is oxidized with mixture of H,SO, (53°) and MnO, at temp. of 60-70° or just 
below the temp. at which bubbles of escaping CO, give evidence of too active oxidation. The 
acid and MnO, are added in small quantities so as to assist in control of temp. and generation of 
CO,. Artificial cooling is required. 


1,367,898—Feb. 8, 1921. Frank A. Strauss, Pennsylvania. 
Production of nitriles and acids. Benzo nitrile and benzoic acid in larger yields. 


BENZENE sulfo, Na salt, and NaCN in mol. proportions are mixed with about 70 per cent 
inert material such as sand of 40 mesh. and heated sufficiently to start reaction. Instead of 
using pure materials with sand, commercial forms of cyanids (Na, Ba, K.) contain sufficient 
inert material as impurities. Sulfo derivs. of other aromatic hydrocarbons and ferrocyanides 
may be used. 


1,368,7S89—Feb. 15, 10921. Henry Dreyrus, Switzerland. 
Process of making acetic anhydrid. Acetic anhydride by simpler process with high 
yield. 


The production of acetic anhydride from a dry acetate and SO, or H,SO, and SO,Cl OH. 
etc., in liquid diluent such as acetic anhydride or acetic acid, as shown in 1,283,115 is improved 
by preparing addition products of SO,, with salts such as NaCl (NaSO,Cl) or Na,SO, (Na,S,0,) 
etc., cooling and adding the prepared salt in mol. proportions to dry pulv. acetate in suitable 
diluent, keeping temp. low, then warming to 60-70°. Reaction between SO, and a salt is ex- 
othermic and by combining these first and cooling before mixing with the acetate injurious temps. 
and secondary reactions are avoided. 


1,369,383—Feb. 22, 1921. Carl Boscu, Germany. (Chem. Found.) 
Compound of urea. (Process also claimed.) Compound of urea and calcium nitrate that 
will not deliquesce. 
Urea and Ca(NO,), are mixed in proportions of 1 to 4 mols. in aq. soln. and dried, or 
mixed in boiling aq. and cryst., avoiding long exposure to high temp. 


1,374,695—Apr. 12, 1921. } 
J. M. Weiss, New York, and C. R. Downs, New Jersey. (Barrett.) 
Catalytic oxidation of fluorene. | 
Mixture of FLUORENE vapor and air is passed at temp. of 300—-700° thru tubes containing 
vanadium oxide deposited on crushed pumice. Mixtures of oxygen with other diluents, other 


372 DIGEST OF PATENTS 


Catalyzers, and variations of temp., pressure, time of contact and other conditions of reaction. 
may be used. 


1,374,721—Apr. 12, 1921. Charles R. Downs, New Jersey. (Barrett.) 
Process of producing anthraquinone. Anthraquinone by improved process. 


ANTHRACENE vapors mixed with an oxygen containing gas are brought in contact with a 
suitable catalyst such as vanadium oxide, regulating the temp. at 375° by means of an ap- 
paratus (drawings and description given) so designed that the heat of reaction is continuously 
absorbed by transference to the lower ends of closed tubes within the reaction zone, which 
tubes contain a liquid such as mercury, under any desired pressure to regulate its boiling point, 
thus allowing its latent heat of vaporization to be employed as a heat-absorbing medium. 


1,374,722—Apr. 12, 1921. Charles R. Downs, New Jersey. (Barrett.) 


Catalytic oxidation of naphthalene. Phthalic acid anhydride, benzoic acid, naphtho- 
quinone, etc. 

NAPHTHALENE is partly oxidized by bringing its vapors mixed with an oxygen containing 
gas, with or without diluent, into contact with Al,O, as a catalyst at 350-700°. (preferably 450°). 
Products may be made in varying amounts by regulating conditions, such as temp., pressure, 
time of contact with catalyst, relative proportion of catalyst, and of naphthalene, oxygen, diluent 
gases, etc. 


1,375,701—Apr. 26, 1921. Carl JAGERSPACHER, Switzerland. (Basle.) 
Azo dyestuffs dyeing on mordants._ 1.8-Dioxy naphthalene 3-sulfo 6-carbo acid. 


NAPHTHALENE 5.7-disulfo 2-carbo, derived from corresponding naphthylamin disulfo acid 
by substituting a CN group for NH, and saponifying, dissolved in H,SO,, (65°) cooled to 25° 
and HNO, (40°) added. Nitro deriv. is reduced by Fe filings and Fe salt of 1-NAPHTHYLAMIN 
6.8-disulfo 3-carbo acid separated, converted to disodium salt, diazotized, boiled in aq., neut. with 
Ca(OH),, converted to 1.8-naphthosultone 6-sulfo 3-carbo by Na,CO,, evaporated, NaOH added 
and heated at 185-190° in autoclave, made acid, SO, boiled off and product salted out. 


1,375,972—Apr. 26, 1921. Arthur G. Perxins, England. (British Dyes.) 
Manufacture of anthranol. Anthranol. ‘ 


Commercial ANTHRAQUINONE added to 1 part glucose or other carbohydrate in 10 parts 
28-30 per cent NaOH is heated in closed vessel to 230° tor 5-10 hours, soln. diluted and Alt. 
Product is pale yellow. 


1,380,277—May 31, 1921. 
J. M. Wetss, New York, and C. R. Downs, New Jersey. (Barrett.) 
Catalytie oxidation of ortho-cresol. Salicylic acid and aldehyde from 2-cresol. 


Mixture of 2-cRESOL vapor and air is passed thru tubes containing molybdenum oxide dis- 
tributed on pumice, and maintained at temp. of 250-500°. Variations in all conditions of re- 
action are discussed. 


1,381,2S80—June 14, 1921. Leo F. Curporarer, New York. (National.) 


Manufacture of naphthols. (Product also claimed.) Basic sodium naphtholate for pro- 
duction of naphthols. 


NAPHTHALENE 2-sulfo, Na salt, is fused with 4 mols. NaOH at 280-325° until two layers 
form, the lower containing sod. sulfite as ppt. and the upper after decanting and cooling, forming 
a yellow, cryst. solid, sol. in aq. and alc. This is called basic sodium naphtholate, and is 
probably a double comp. of sulfo acid salt with NaOH. 


1,382,196—June 21, 1921. Carl JAGERSPACHER, Switzerland. (Basle.) 
Azodyestufiz dyeing on mordants.  1-Naphthol 3-sulfo 6-carbo acid. 


NAPHTHALENE 5.7-disulfo 1- or 2-carbo, derived from 1 or 2-NAPHTHYLAMIN 5.7-disulfo 
by substituting CN for NH, and saponifying, is heated at 195° in autoclave with 40 per cent 
NaOH, and 1-naphthol 3-sulto 5- or 6-carbo acid pptd. from soln. by HCl, 


1,384,615—July 12, 1921. Fritz Hanserrc, Austria. 
Art of manufacturing perylen. ; 


Equal parts 2-DINAPHTHOL and H,PO, are heated quickly to 500° while 1 part PCI, is 
added. Other ortho substituted comps. such as 2.2/-dichlor 1.1/-dinaphthyl can be used with or 


GROUP XXII.—INTERMEDIATES 375 


without flux which increases yield. AICI, may be substituted for PCI, to close ring in second 
part of reaction. 


1,384,909—July 19, 1921. Chauncey C. Loomis, New York. (Semet-Solvay.) 
Art of halogenating hydrocarbon compounds. Halogenation in side chain. 

TOLUENE in which o.5 part Na,CO, is suspended is treated with rapid current of Cl. 
Temp. rises as reaction proceeds and to prevent nuclear chlorination should be held at 60—-70°. 
When carbonate is used up mass becomes hard, then Cl is cut off. NaCl and NaHCO, are 
dissolved out and residual oil will be found to contain benzyl chloride and toluene. This may 
be further chlorinated to di and tri chlor derivs. Process is of general application. 


1,386,118—Aug. 2, 10921. William E. Kirst, Michigan. (Dow.) 
Manufacture of chlorhydrin. Separating chlorhydrin from water. 

Benzol is added to the aq. CHLORHYDRIN mixture, which is distilled and as the combined 
vapor tension of water and benzol is greater than atmospheric pressure at a temp. below the 
b.p. of chlorhydrin or water alone, the mixture of benzol and aq. will boil off and with excess 


benzol the last traces of aq. may be removed. Then the benzol will readily distill off and may 
be reused. 


1,388,016—Aug. 16, 10921. Walter Bauer, Germany. (Rohm.) 
Manufacture of alkylene cyanhydrins. : 
Conc. soln. of KCN or NaCN is added to ETHYLENE bromhydrin or chlorhydrin keeping 


temp. at 55-60° or at 45° respectively, ethylene cyanhydrin washed with ether and fractionated. 
Yield is 85-90 per cent 


1,390,241—Sept. 6, 1921. 
J. A. Amsier, Connecticut, and H. D. Grszs, California. (U. S. Govt.) 
Process for the manufacture of naphthalene sulfonic acids. Naphthalene 2.7- 
disulfo or other naphthalene sulfo acids. 
Process and apparatus are similar to 1,300,227, using H,SO, (1.84) and temp. of 220-230°. 


Reduced pressure and corresponding temps. may be applied by necessary modification in the 
apparatus. 


1,392,942—Oct. 11, 1921. Arthur E. Hovreuan, Delaware. (du Pont.) 
Process for the manufacture of diphenylamin. Diphenylamin from anilin. 
Process and apparatus (drawings shown) are similar to 1,314,538, using 1-4 per cent of 


NH,I as catalyst and temp. of 275-300°. About 1 per cent aq. (0.75-2.00 per cent) mus* be 
present. Variations in process and apparatus may be made. 


1,393,191—Oct. 11, 1921. Jean AxLtwecc and Joanny Lanprivon, France. (Soc. Chim.) 
Process for the manufacture of ethereal salts of ethylenic halogenhydrins. 
b-Chlor ethyl acetate, chlor acetate, benzoate or nitro benzoate and brom derivs., etc. 


Gaseous ETHYLENE oxide is passed into boiling acrety, chloride or bromide or BENZOYL 
chloride, etc., in moleculer proportions. 


1,393,597—Oct. 11, 1921. Talbot J. ALpert, Jr., Delaware. (du Pont.) 
Process of producing tetra-substituted ureas. Dimethyl diphenyl urea or other. 


Methyl anit1n and 0.62 parts Na,CO, are mixed in 1.24 parts aq. and well stirred while 
COCI, is passed in until 5 per cent in excess of theoretical amount required. Mixture is then 
heated at 95-99° for 2 hours. Other aryl alkyl amins and alk. reducing agents that do not 
readily react with COCI, under given conditions may be useda 


1,394,150—Oct. 18, 1921. 
C. G. Derick, W. M. Rateu and L. H. Frerr, New York. (National.) 


Production of m-nitro-p-cresol. 3-Nitro 4-cresol. 


One mol. 4-ToLuIDIN is dissolved in about 6 parts 38 per cent H,SO, while hot, diluted 
with 10 parts ice, diazotized with excess NaNO,, and a little more than 1 part NaNO, added. 
Soln. is run slowly into a vat, the first portion heated to 65° to start reaction, and temp. 
maintained at'6s5° by heating or cooling as required. The effect of variations in conditions of 
reaction is discussed in detail. Mother liquors are reused. 


374 DIGEST OF PATENTS 


1,394,556—Oct. 25, 1921. Whitney B. Jonrts, New Jersey. (Butterworth.) 


Process of making nitrodiazo compounds. Nitration of diazo comps., stabilized by 
use of metal double salt. 


Zinc salt of diazo I-AMINO 2-NAPHTHOL 4-sulfo as fine dry powd. is added slowly to 3 
parts H,SO, monohydrate below 5°, mixed acid slowly added, keeping same temp., mixture 
diluted, filt. and resulting paste used direct for azo dye mfr. 


1,394,664—Oct. 25, 1921. Benjamin T. Brooxs, New York. (Chadeloid.) 
Process of making chlorhydrins. 


Apparatus is shown wherein chlorine and petroleum still gases are passed in molecular 
proportions into an emulsion of 2-10 per cent salt and 2-5 vols. of an immiscible solvent such 
as paraffin oil, chlornaphthalene CCl,, C,H,Cl,, etc. at 10-20°, and above atmospheric pressure, 
the solvent and accompanying chlorhydrin being removed from reaction chamber before further 
chlorination is effected, and separated. Conditions of reaction are discussed in detail. 


1,894,851—Oct. 25, 1921. Arthur Lurtrincuaus and IL. E1FFLaANpER, Germany. (Kutrow.) 


Manufacture of anthraquinone derivatives and new products resulting 
therefrom. Aryl 1-amino 2-methyl anthraquinone, the 2 amino, bis aryl amino or other 
derivs. 


1-Amino 2-methyl ANTHRAQUINONE, or deriv., is heated to 50° in 15 parts ANILIN or other 
primary aromatic amin, air in vessel replaced by an inert gas such as N, 0.63 parts sodamid added, 
temp. raised to 60-65° and dye pptd. by excess of dil. HCl. Air passed through reaction mixture 
increases yield. A metal arylid is formed which converts amino anthraquinone into the desmo- 
trope quinoid form to which the aryl amin then attaches itself. Products are sol. in conc. sulf. 
(B), in glac. acetic (VR). 


1,395,620—Nov. 1, 1921. C. Weizmann and D. A. Lecce, England. 
Manufacture of hydrocarbons. Naphthene by polymerization from butene and butyl 
alcohol. 


Vapor of normal primary Buty alcohol at atmos. pressure is passed thru tube containing 
Al,O, distributed on pumice at temp. of 250-320°. Products are 80 per cent 2-BUTENE and 20 
per cent 3-BUTENE. Increase of temp. gives more 2-butene up to 390° when this isomer is 
sole product. The 2-butene is catalyzed in liquid state with anhyd. AlCl, or FeCl, (about 2 per 
cent) at temp. of 10°, or higher when pressure is applied. 


1,396,320—Nov. 8, 1921. Robert M. Coit, Ohio. 


Method of obtaining a sodium salt from a hydrocarbon monosulfonie acid. 

Carvacrol from 4-cymene, sodium sulfo acids for phenol production, etc. 

Sulfonation is made by usual process using, however, an excess of the hydrocarbon, 
then NaCl or other highly ionizable salt is added whereby double decompn. produces free 
hydrocarbon, free acids, (H,SO, and HCl), chloride, sulfate and ppt. of sodium hydrocarbon 
sulfonate. 


1,396,913—Nov. 15, 1921. Walter Baprr, England. (Levinstein.) 
Production of aminoalkylesters and of alkylaminoalkylesters of para 

amino-benzoiec acid. Aluminum comp. of reacting alcohol as condensing catalyst. 

Equal parts 4-amino BENzoIc acid, ethyl ester, and diethyl amino EtTuyt alcohol with 1-2.5 per 
cent aluminum comp. of the latter are heated at 150-180°, the ethyl alcohol produced being dis- 
tilled off. When this ceases, pressure is reduced to 27-28 inches and at 170° the excess diethyl 
amino ethyl alc. is distilled off and recovered as HCl salt, unchanged benzoic ester is removed by 
filtration and product pptd. by NaOH, etc. 


1,397,913—Nov. 22, 1921. Thomas B. Atupricu, Michigan. (Parke, Davis.) 
Benzoic-acid esters of tribromotertiary butyl alcohol, 


One part tribrom tertiary sutyL alcohol is heated at 100° with 1 part BENzoyL chloride until 
HCl ceases to evolve then oil separated by diln. Derivs. are claimed. Products are relatively 
stable, insol. in aq. and easily sol. in organic solvents. 


1,400,555—Dec. 20, 1921. Kaichi Kasat, Japan. (Mitsui.) 
Manufacture of paranitroanilin from paranitroacetanilid. 4-Nitranilin from 
4-nitroacetanilid in better quality and more economically. 


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GROUP XXII.—INTERMEDIATES 375 


4-Nitro ACETANILID, NaOH and aq. are mixed in proportion of 25: 5:70 and heated at 120- 
130° and 25 lbs. pressure. A go per cent yield of cryst. 4-nitranilin is claimed. Live steam 
may be introduced as heating agent and correspondingly less aq. used in first mixture. 


1,401,125—Dec. 27, 1921. Frederick W. Aracx, England, and George Rosrrrson, Scotland. 
Halogenation of anthraquinone derivatives. 1-Halogen 4-oxy anthraquinone, or 
derivs. 
1-Oxy ANTHRAQUINONE, or deriv., is heated in nitrobenzene containing Na,CO, or other neut. 


agent and iodine or other carrier, and chlorine or bromine passed in until a sufficient weight 
has been absorbed. 


1,401,937—Dec. 27, 1921. George C. Bartry, New Jersey. (Barrett.) 
Purification of maleic acid by reducing agents. Production of pure white maleic 
acid. 


In the catalytic oxidation of BENZENE to benzoquinone as given in 1,318,633 the varying 
amounts of maleic acid produced as by-product are contaminated by colored oxidation comps. 
Current patent employs an alk. sulfite in the receiver or SO, vapors are conducted therein where- 
by the BENZOQUINONE is immediately reduced to hydroquinone, which will not decomp. to dark 
colored comps. in presence of excess SO,. Sod. salt of maleic acid is recovered as white crysts. 
while SO, vapors are collected and reused. 


1,403,920—Jan. 17, 1922. Charles J. Srrosacker, Michigan. (Dow.) 
Method of making acetic anhydride. 

To 2 parts dry sod. acetate in vessel at 20 lbs. pressure is gradually added 1 part SCl.,, 
keeping temp. at 20°. Reaction is practically instantaneous. Vacuum is then applied and acetic 
anhydride distilled over up to 110°. By-products such as acetic acid, SO,, etc., are small in 
amount, 


1,404,055—Jan. 17, 1922. Emil Portueim, Czecho-Slovakia. (Kinzlberger.) 
Purification of crude anthracene. Anthracene above 98 per cent purity, and carbazole. 


Crude ANTHRACENE, (50-53 per cent) is purified by soln. in naphtha (b. p. 145°) and 70 
per cent product is boiled with KOH (75 per cent) in naphtha (b. p. 145°) so long as aq. comes 
over, replacing loss of solvent. Carbazole potassium separates as heavy sandy ppt. and may be 
treated with steam to recover KOH and carsazouE. Larger proportions of alkali result in more 
complete separations by removing water from reaction. 

Note 1,404,056. 


1,404,056—Jan. 17, 1922. Emil Porruemm, Czecho-Slovakia. (Kinzlberger.) 
Process for the purification of anthraquinone. Anthraquinone of 99.5 per cent 
purity. 

Crude ANTHRAQUINONE (90-91.5 per cent) is boiled in chlorbenzene, coal tar naphtha (b. p. 
126-130°) or other-neutral solvent, containing NaOH (solvent and aq. slowly distil over) until 
sample when heated in a clean portion of reagent does not darken it. Sulfuric acid 60° may also 
be used as purifying agent. Anthraquinone is pptd. on cooling and removed. Chlorbenzene, etc., 
may be recovered. 

Note 1,404,055. 


1,405,261—Jan. 31, 1922. 
C. O. Benepetti, A. P. VansELow and W. VansEtow, New York. 
Process of the production of aromatic aldehydes and their substitution 
derivatives. Benzaldehyde from benzylchloride, etc. 

Benzyz chloride is refluxed in 6 per cent NaOH for several hours and about 0.65 parts 
of a soln. containing 18.6 per cent NaOCl with excess NaOH (not more than 2-3 per cent) is 
added slowly, while soln. is distilled. Bxnzyx alcohol produced in first reaction is oxidized to 
BENZALDEHYDE which, being more volatile with steam is distilled off before decomp. can take 
place while benzyl alcohol remains in reaction vessel until completely oxidized. Drawings of 
apparatus and detailed discussion of points in process are given. 


1,405,732—Feb. 7, 1922. William H. Maunter, New Jersey. 
Method of deriving hydrazobenzol and its homologues. 


One mol. NITROBENZENE is added to 2.85 parts 14.5 per cent NaOH in rotating drum fol- 
lowed by 1.62 parts zinc in granular or other form having small surface area as compared 


376 DIGEST OF PATENTS 


with filings, and mixture well agitated. A temp. of 98° is reached without extraneous heat and 
when temp. falls to 50° reaction is complete. Advantages of method are detailed and homologs 
claimed. Yield of derived benzidin is 80 per cent. 


1,405,954—Feb. 7, 1922. Charles J. Tuatcner, New York. 
Process for utilizing waste liquor. Improved chromic acid process for anthraquinone. 

Spent chrome liquors from previous operations, while hot are divided into two portions, 
one of which is used instead of aq., for new charge of anthracene and the other is regenerated 


electrolytically, then added to first portion and reused. Expensive condensation of large volumes 
of liquids is avoided. 


1,406,745—Feb. 14, 1922. Harry McCormack, Illinois. 
Manufacture of resorcinol. 

BENZENE sulfo acid, prepared by sulfonation of BENZENE with fuming H,SO, (20 per cent 
SO,) at 70°, is further sulfonated at 225° to disulfo deriv., converted to sod. salt, separated 
and fused in 2 parts NaOH at 315° for 2 hours. Melt is dissolved in sufficient hot aq. so 
that on cooling Na,SO, will cryst. out almost completely, separated soln. is neut. with H,SO,, 
cooled, Na,SO, crysts. removed, residual soln. is evap. dry and extracted with organic solvent 
for resorcin or is dry distilled to sublime the product. 


1,409,588—Mar. 14, 1922. Walter Runcre, New Jersey. (Inter. Coal.) 
Obtaining tar acids. 
Distillates of tar containing acids are extracted with NaOH, decanted, and CO,, blue gases, 


etc., passed in under pressures of preferably 100 pounds. Apparatus is shown and described 
and claims are made mainly for use of pressure when introducing CO,. 


1,409,897—Mar. 14, 1922. 
Walter B. Murpuy and Wilbur G. Dunninc, Pennsylvania. (Barrett.) 
Sublimation of hydrocarbons. 

Crude ANTHRACENE is sublimed in closed vessel at 270° and vapors carried by steam are 
introduced below surface of molten anthracene or blown across surface at a temp. of 220-250° 
into a second chamber where a blast of air suddenly expands the mixture from too lbs. to 
atmospheric pressure at a temp. that retains the moisture but deposits the anthracene as an 
extremely fine powd. The first and last portions of the sublimate contain light and heavy 
impurities and are collected in one receiver while middle portion consisting of pure anthracene, 
is collected in a second receiver. 


1,410,494—Mar. 21, 1922. Robert Meyer; France. (Poulenc.) 
Manufacture of diaminoacridine. 3,.6-Diamino acridin in one process. 

3-PHENYLENE DIAMIN is melted with FoRMIc or oxalic acid with assistance of GLYCERIN or 
other polyhydric alcohol and a condensing agent such as ZnCl, or CaCl, at a temp. of 130° and 


when CO, ceases to evolve temp. is kept at 150-170° for 2 hours. Melt is heated with aq. and 
NH, to ppt. diamino acridin. 


1,411,529—Apr. 4, 1922. Noel Statuam, New Jersey. (West Virginia Pulp.) 
Apparatus for dry distillation. Acetone, etc. : 

Apparatus is drawn and described for dry distillation of acetates (Ca, Na, etc.) by which 
charge may be uniformly and gradually heated, continuously agitated within a rotating retort 


under conditions to secure favorable heat treatment and minimize local overheating and loss of 
desirable volatile products. 


1,411,683—Apr. 4, 1922. Hans T. CiarKe and William W. Hartman, New York. (Eastman.) 
Process of manufacturing acetyl mono-methyl aryl amines. 


AcetyL chloride and dimethyl ANILIN mixed in mol. proportions are added in fine stream 
to reflux apparatus containing dimethyl anilin or a mixture of this with methyl acetanilid 
which is held at temp. of about 190° (b. p. of mixture). Methyl chloride escapes and when 
sufficient methyl acetanilid has formed, bath mixture is cooled and cryst. product removed by 
filtration, bath is renewed and process continued. Homologs are claimed. 


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GROUP XXII.—INTERMEDIATES CUS 


1,413,494—Apr. 18, 1922. Homer Rocers, Delaware. (du Pont.) 
Method of producing alkyl anilines. 


One mol. each of ANILIN and METHYL alc., mixed with about 0.01 mol. or 0.71 per cent of 
methyl iodide as catalyst are digested at an elevated temp. until two layers form, one of 
crude dimethylanilin and other containing excess alc., water, and trimethyl phenyl ammonium 
iodide. The latter, derived from dimethyl anilin and methyl iodide, is a catalyst for the re- 
action, and is repeatedly recovered. 


1,414,441—May 2, 1922. 
Frederick W. Sperr, Jr., and Ralph L. Brown, Pennsylvania. (Koppers.) 
Recovery of pyridine from ammonium sulphate solutions. Conserving pyridin 
as by-product in dry distillation of coal. 


PyrRIDIN is recovered from (NH,),SO, liquors while acid by passing crude vapors into 
the saturator until pyridin is‘no longer absorbed, reducing the acid content to about 2 per cent, 
saturating the soln. with (NH,),SO, at its boiling point, and steam distilling the pyridin. Ap- 
paratus contains a plurality of saturators so that stream of crude gases may be deflected from 
one to another during recovery of pyridin. Drawings of apparatus shown and advantages given 
in detail. 


1,416,205—May 16, 1922. Wilbert J. Hurr, Pennsylvania. (Koppers.) 
Dehydration. Dehydrating liquids of constant b.p. lower than that of the essential con- 
stituent. 


PyRIDIN-aq. or similar mixture is first salted out, then is distilled until constant boiling point 
mixture comes off. Distillate is partly dehydrated with cheap agent such as anhyd. (NH,), SO,, 
returned to still and process repeated until material in still is substantially fully dehydrated. 
The fraction boiling above 115° is anhyd. 


1,416,206—May 16, 1922. Wilbert J. Hurr, Pennsylvania. (Koppers.) 
Dehydration of pyridine. 


The principle of the dehydration is same as in 1,416,205 but a comparatively low boiling 
liquid such as a PETROLEUM distillate boiling at 80° which is immiscible with aq. and miscible with 
anhyd. pyridin is added to mixture to serve as a vehicle to carry off water. Repeated partial 
distillations, drying of distilled portion, and returning to still are carried out as in previous 
process. The amount of low boiling liquid added must not be sufficient to form a binary con- 
stant boiling point mixture with all the water present. 


1,416,284—May 16, 10922. Arne Gopat, Norway. 
Process of producing sulphoaromatie substances for use in the decomposi- 
tion of fats. 

A fatty acid such as oLrErc acid is mixed with an aromatic comp. such as NAPHTHALENE in 
equimol. proportions in a solvent like benzol so as to produce a clear soln. Sulfuric acid is 
then added, below 5° and when product is aq. sol. it is allowed to rest 12-24 hours, then re- 
peatedly poured in thin stream into water, kept below 5°, each time allowing water layer to 
separate and be drawn off. ‘This acid water contains aromatic sulfo acids which are recovered. 
The sulfo fatty acids are separated by soln. in aq., concd. by evapn. under reduced pressure 
and unchanged oleic acid and naphthalene recovered with solvent benzol. 


1,417,277—May 23, 1022. Otto Nyprccer and Henry SHELLENBERG, Switzerland. 
Process of producing urea from lime nitrogen. Urea from Ca(CN), using acid and 

Ca(NO,), as catalyst. 

Calcium cyANAMIp is added slowly (within 30 m.) to ro parts 20 per cent HNO, below 
20°. After 4 hours 50 per cent and after 15 hours all has changed to urea. When lime 
nitrogen is slowly added to 5 parts Ca(NO,), soln. (1.5) together with 3.25 parts HNO, (40°) 
below temp. of 30° the entire change takes place in 15 m. 


1,417,367—May 23, 1922. 

: C. Conover, Pennsylvania, and H. D. Grass, California. (Selden, %.) 
Process for the manufacture of anthraquinone. Anthraquinone. 

ANTHRACENE vapors mixed with excess air, oxygen, or inert gas mixtures containing oxy- 
gen, are passed through a catalyst such as vanadium oxide, at a temp. of 350-550° (preferably 
500°). Kind and condition of catalyst, proportion of ingredients, and contact methods, etc., may 
be varied within wide limits. 


378 DIGEST OF PATENTS 


1,417,368—May 23, 1922. Tenney L. Davis, Massachusetts. 


Mercury nitrate as a reagent for the preparation of nitrophenols. (Process 
only claimed.) 


The mercury salt in preparation of nitro PHENOLS, or other, does not function as a catalyst 
but enters the chemical reaction. Molecular proportions of mercury salt are therefore used and 
resulting comp. decomp. by HNO,. Higher yields are obtained, 


1,417,369—May 23, 1922. Tenney L. Davis, Massachusetts. 


Proeess for the preparation of guanidine. Guanidin, salts and derivs. from di- 
cyandiamid in pure condition, free of excess acid, or NH, salts, etc. 

DICYANDIAMID, derived from Ca cyanamid, which in turn is produced from CaC, and N of 
air, is heated at 160° in autoclave with 1.25 parts aq. NH, (0.90) for 1 hour then excess NH, 
blown out by air or steam. The guanidin carbonate that remains in soln. may be recovered as a 
‘deriv. or as the salt of any desired acid. 


1,417,875—May 30, 1022. Karl Wiixkt, Germany. (Hochst.) 


Anthraquinone derivatives and process of making same. ‘Methyl 1.2-anthra- 
quinone isoxazole and derivs. 


1-Nitro 2-methyl ANTHRAQUINONE, the 1.5-dinitro or other deriv., mixed with 20 parts quartz 
sand is made with fuming sulfuric (40-60 per cent SO,) into a stiff magma, diluted with ice, etc., 
and freed from sand by boiling in xylene. Air is excluded during reaction. Properties of some 
products are given. 


1,419,124—June 6, 1922. Walter F. Rittman, Pennsylvania. (Hydrocarbon.) 


Treatment of xylene and other similar hydrocarbons. ‘Toluene from xylenes 
or solvent naphtha. 


Apparatus is drawn and described whereby higher boiling point hydrocarbons are fed by 
gravity or forced into the upper portion of a reaction chamber where they pass over balls of 
metal supported on a perforated disk down into the chamber in which preferably a pressure 
of 0.5 atmos. and temp. of 600—-900° is maintained. With pure xylene above 30 per cent toluene 
has been obtained with less than 1 per cent carbon. 


1,419,157—June 13, 1922. Egil Lit, Norway. 
Producing urea from cyanamide, 

Equal parts CcyANAMIp and Ca(NO,), or other nonacid salt and 0.2 parts aq. are heated at 
125-130° whereby an 83 per cent yield in less than 1 hour is obtained and loss of NH, slight. 


Yields vary with temp., amount of aq., ratio of components, pressure and time of reaction as 
well as salt or catalyst employed. Too high temps. give NH, and other decomp. prods. 


1,419,186—June 13, 1922. Leopold Writ, Germany. 
Process of producing high-percentage pure anthracene. Anthracene of 73-80 
per cent purity. 
Crude ANTHRACENE (25 per cent), mixed with 0.375 part gas oil (Sp. Gr. 0.84, b.p. 260- 
315°), is distilled and, by automatic feeding of the solvent oil, decomposition by overheating is 


avoided. Anthracene in distillate is separated by cooling and filtering and the solvent is re- 
covered and re-used. 


1,419,695—June 13, 1922. John B. Stimm, New York. (National.) 

Production of meta-hydroxybenzaldehyde. Oxy-benzaldehyde from 3-nitro-benz- 
aldehyde without isolation of intermediate products and with increased yield and quality. 
Nitro BENZALDEHYDE and NaHSO, (0.83 parts) are dissolved in aq. with heating, reduced 

with Fe dust and small amount HCl added in several charges at increasing temps. (45°-60°— 


80°-86°) cooled, diazotized and poured into excess acid soln. at 100°, filt. and salted out. Nitro- 
gen and SO, are removed simultaneously. 


1,420,198—June 20, 1922. Harry F. Lewis, New York. (National.) 
Purification of anthraquinone, Anthraquinone of 90-95 per cent purity. 


Crude ANTHRAQUINONE extracted at 20-60° with mono-chlor benzol or other halogen hydro- 
carbon, which, acting as a selective solvent, removes the impurities. 


GROUP XXII.—INTERMEDIATES 379 


1,420,346—June 20, 1922. Walter O. SNELLING, Pennsylvania. 
Photochemical process. Chlorination of hydrocarbons by photochemical process. 
Apparatus is shown consisting of dome shaped cells into the middle of which a current of 
mixed hydrocarbon and halogen vapors is introduced, rises as reaction goes on, impinges on the 
curved top and as it travels down the sides gives off heat to walls of vessel then passes out at 
the side, of the lower part of container. Temp. can be so reduced that direct sunlight or other 
strong actinic rays may be applied without danger of reaction taking place with explosive violence. 


1,421,604—July 4, 1922. John A. Srerrins, Maryland. (U. S. Ind. Alc.) 
Process for the manufacture of esters. 

Apparatus is shown whereby an alcohol and acid may be esterified in presence of a third 
liquid such as benzol, etc., that is miscible with the alcohol but not with aq. Vapors are evolved 
in form of a ternary mixture, the layer containing a small percentage of third liquid is rectified 
and remaining ester is distilled under vacuum to remove alcohol and third liquid. 


1,421,605—July 4, 1922. John A. Srerrens, Maryland. (U. S. Ind. Alc.) 
Process for manufacturing esters. 


Apparatus is shown and process is similar to 1,421,604 except that catalysts such as H,SO,, 
HCl, H,PO,, ZnCl, or NaHSO,, are used. 


1,421,743—July 4, 1922. Bernhard C. Srurep and Walter Gros, Germany. 

Process for the manufacture of products from acetylene. (Product also claimed.) 
Acetaldehyde and other products of synthesis of acetylene with N, O or S using inexpensive 
catalysts. 


ACETYLENE mixed with 4 parts steam is passed at 400-420° over bog iron ore and product 
condensed. The 15-16 per cent acetaldehyde collected after one passage over catalyst can be 
increased by repeating the process. Using NH, or H,S instead of steam yields aceto nitrite, mer- 
captan, etc. Each main product is accompanied by a‘ variety of side products. Materials and 
methods of preparation of catalyst are given in great detail with effects upon reaction by vary- 


ing conditions. 


1,422,183—July 11, 1922. George O. CurmMg#, Jr., Pennsylvania. (Union Carbide.) 
Process of treating gaseous mixtures. Isolating definite components of gaseous 
mixtures. . 


Apparatus is shown wherein a mixture of gases may be compressed, passed into contact with 
a solvent, undissolved components are collected and solvent rectified to recover special com- 
ponent desired. Temps. are maintained below and pressures above atmospheric. 


1,422,494—July 11, 1922. Arthur P. Tangerc, Delaware. (du Pont.) 
Method of manufacturing diphenylamin. Diphenylamin from anilin and a catalyst. 


Apparatus is shown whereby ANILIN may be heated at about 300° under pressure with 
chlorine as catalyst (0.5-3 per cent) either as HCl or preferably as a chloride. About 1 per 


cent water must be present. 


1,422,564—July 11, 1922. A. R. Gros and C. C. Apams, Delaware. (du Pont.) 
Process of sulfenating carbon compounds. 


BENZENE or other aromatic comp., is dissolved in liquid SO, at 10° and reduced pressure, 
and to this is added a soln. of SO, in SO, at about 0°, then temp. raised to 20° and to 30°, 
still under reduced pressure. Heat is applied finally to remove SO,, leaving excess SO, and 
sulfo acid as thick residue. Temps. and pressures may vary widely. 


1,422,889—July 18, 1922. Karl ScHIRMACHER, Germany. (Metz.) 
Manufacture of 9.10-dihalogen anthracene-S-monosulphenie acid. 9.10-Di- 
halogen anthracene 2-sulfo acid. 


9.10-Dichlor or dibrom ANTHRACENE suspended in about 4 parts nitrobenzene to which is 
added slowly at 10-15° 2 parts of fuming (20 per cent) sulfuric diluted by same solvent. Product 
forms fine needles of yellow tint, m.p. 193°, sol. in aq. with strong blue fluorescence. 


1,423,494—July 18, 1922. Louis Haas, France. (Parisse.) 
Process for the preparation of aromatic nitramines. Nitramines from chlor de- 
Tivs. at low temp. 
25 


380 DIGEST OF PATENTS 


Acetic acid of 80-95 per cent strength is satd. with dry NH, which causes temp. of 125-130°, 
and 2.4-dinitro chlor BENZENE is introduced gradually at this temp. while NH, gas is passed in 
continuously to replace that which has entered reaction and regenerate amm. acetate for recovery 
and reuse. Other mono, di, or trichlor nitro derivs. that will react with NH, are claimed. 


1,423,980—July 25, 1922. Arthur G. Witirams, New Jersey. (Barrett.) 
Production of dicarboxylic acids. Oxidation of ortho dioxy or diketo groups to di- 
carbo acid. 


PHENANTHRAQUINONE is warmed so as to dissolve in ro parts 20 per cent NaOH and 2 
parts sod. hydrosulfite, cooled on ice and mixed with 4.5 parts Na,O,, warmed to 40-5o0° until 
green color disappears, filt. and pipHENIC acid pptd. by HCl. Yield is 86.2 per cent. Other 
dicarbo acids are produced from ortho diketones or double bonded dioxy groups within a cyclic 
ring structure. 


1,425,392—Aug. 8, 1922. 
August L. Lasxka and Hans H. C. Prituwitz, Germany. (Griesheim.) 
New liquid phosphoric esters and processes of making same. Phosphoric acid 
esters of benzene series with methyl group in other than para position to oxygen, at least 
two constituents being different. 


3-CrESso~ or other phenol deriv., and POCI, are heated until HCl ceases to evolve, then 
again heated with 3- or 4-CRESOL at gradually ascending temps. until no vapors of HCl escape. 


1,425,393—Aug. 8, 1922. 
August IL. Laska and Hans H. Prituwitz, Germany. (Griesheim.) 


New mixed phosphoric esters and processes of making same. 


Patent is similar to 1,425,392, using crude phenols and cresols, etc., containing at least 
25-30 per cent of a phenol with an alkyl group in other than para position to the oxygen. 


1,425,500—Aug. 8, 1922. H. W. Marueson and G. E. Grattan, Canada. (Shawinigan.) 
Manufacture of acetic anhydride. 


Apparatus is shown whereby acetic anhydride is formed in one step by action of ACETYLENE 
gas on com’l. acetic acid (96-100 per cent) in presence of finely divided salt of Hg. (HgO, HgSO,, 
etc.) under atmospheric or superatmospheric pressure and at temps. of 60-200° according to 
pressure used. By an arrangement of traps, condensers at definite temps. and return pipes the 
excess acetylene, acetic acid, acetone, Hg, etc., are separated. 


1,425,625—August 15, 1922. Arthur A. Backuaus, Maryland. (U. S. Ind. Alc.) 
Process for the manufacture of esters. Ethyl acetate or other esters. 


Apparatus is shown whereby an alcohol and organic acid are esterified by heating in presence 
of a catalyst such as H,SO,, the ester formed and accompanying vapors are continuously dis- 
tilled off, major portions of other constituents are condensed and returned to sphere of action 
and constant boiling vapors are dephlegmated to obtain pure ester. 


1,425,626—Aug. 15, 1922. Arthur A. Bacxuaus, Maryland. (U. S. Ind. Alc.) 
Method for the production of ester condensation products. Ethyl aceto acetate, 
etc. 


Etruyt acetate, 99 per cent, or other ester, and about 4 per cent metallic Na (K or Mg), 


are placed in still and after reaction ceases 10 per cent H,SO, in amt. to combine with Na is 


added. ‘The two layers formed are separated and oily layer distilled to remove excess ethyl 


acetate and residual crude ethyl aceto-acetate is purified by distn. in vacuum. Water layer may — 


be treated to recover alcohol and Na,SQ,. 


1,426,380—Aug. 22, 1922. W. N. Hawortnu and F. W. Atacx, England. 
Manufacture of aromatic alkyl-amino compounds. Alkylation of amino compounds. 


For methylation or ethylation of an amin such as I- or 2-amino ANTHRAQUINONE, 1-naph- 
thylamin, etc., the amin, dissolved in nitrobenzene or tetra chlor ethane or other high b.p. sol- 


vent containing anhyd. Na,CO, or MgO, etc., is refluxed while 1 or 2 mols. DIMETHYL sulfate or — 


homolog is slowly added during 30-45 min. and boiling continued for 30 min. Yield is 87 per 


cent. 


GROUP XXII.—INTERMEDIATES 381 


1,426,457—Aug. 22, 1922. Lloyd M. Burcuart, Maryland. (U. S. Ind. Alc.) 
Process of recovering volatile organic acids from distillery waste. 


Apparatus is shown whereby waste material from distilleries in production of alcohol from 
sugary materials such as molasses are incinerated after causticising, resulting oxalate and as- 
sociated salts are treated with acid water, solids separated, oxalate in soln. pptd. by CaO, sep- 
arated, liquid evap’d., treated with excess non-volatile mineral acid and an alcohol and result- 
ing esters distilled under reduced pressure. 


1,427,215—Aug. 29, 1922. Leon [Tinrenreip, Austria. 
Process of manufacture of dialkyl sulphates. Diethyl sulfate, etc. 


An alifatic alcohol, 2 mols., is treated with 1 mol. SO, in presence of a dehydrating agent 
which will not decompose the product, such as anhyd. Na,SO, or P,O, and distilled in vacuum 
of 25-30 mm. CCl, or other inert solvent may be used as diluting agent. 


1,428,984—Sept. 12, 1922. Julius Scumiptin, Germany. (Cassella.) 


Manufacture or production of chlorinated products of toluene and dyestuffs 
therefrom. (Product only claimed.) Tetra chlor toluene and tetra chlor benzaldehyde. 


Dry TOLUENE is mixed with about 1 per cent anhyd. FeCl, and at 12-15° dry Cl is passed 
Over its agitated surface. When mass thickens with crystals of trichlor deriv. it is heated to 
liquefy and more Cl added at 30-50°. A oo per cent yield of tetra chlor toluene results. This 
is heated to 1o0—-130°, exposed to light and more Cl slowly added and resulting tetra chlor 
BENZAL Chloride heated at 90° in strong H,SO, to convert to the aldehyde. 

See same number among dyes Gr. XVIII. 


1,429,483—Sept. 19, 1922. Carl Boscu and Wilhelm Metser, Germany. (Badische.) 
Process of manufacturing urea. Continuous process for producing urea. 


Mixture of CO, and NH,, preferably moist, is forced by a preheated compressor into an 
autoclave and maintained at 135° for 2 hours at 50-100 atms. slowly released through valve into 
distilling column in which unaltered CO, and NH, are expelled by steam and reused while urea 
runs off at bottom. 

Note 1,344,673. 


1,429,514—Dec. 22, 1920. Harry F. Lewis, New York. (National.) 
Purification of anthraquinone. Anthraquinone of 99 per cent purity. 


Process is same as for 1,420,198, but begins with 88 per cent ANTHRAQUINONE, employs 1.2- 
dichlor benzol (“‘Solvent 74’’) or other halogen hydrocarbon at boiling point, is filtered hot then 
cooled to 10-25°, when a large part of the anthraquinone may be filt. off. Larger proportions 
of solvent at lower temps. are equally effective for removing impurities and additional treat- 
ments will improve product. 


1,429,650—Sept. 19, 1922. F. W. Sxrrrow, Canada. (Shawinigan.) 
Process of manufacturing aldehydes and anhydrides from diesters. Acetic 
anhydride and acetaldehyde in high yield (80 per cent.) 

Crude ETHYLIDENE diacetate liquor is treated with sod. acetate to remove H,SO, and, to- 
gether with all products of reaction including acetic acid and reduced catalyst, is distilled in 
vacuum. Condensate which will contain o.1-0.5 per cent active sulfur comps. is gently boiled 
with rectifying column, keeping temp. at top of column at 40-—60° so that aldehyde and some vinyl 
acetate distill over. After 4-5 hours residue is distilled so as to separate the uncoverted di- 
acetate, acetic anhyd. and acetic acid which remain. An oxide of sulfur may be added but 
should not exceed 1 per cent. 


1,429,714—Sept. 19, 1922. Charles B. Cuatrretp, New Jersey. 
Process of making substituted amines. Alkylation of amins. 


Etuyt bromide is boiled and vapors conducted into a closed vessel containing a mixture of 
ANILIN and 37 per cent NaOH at 85° and atmos. pressure. Entering vapors agitate the liquids 
and, as the mono and di substitution products form, HCl is absorbed by NaOH. Escaping 
vapors are collected and returned. Product is 85 per cent diethyl and 15 per cent mono ethyl 
anilin. 


1,429,953—Sept. 26, 1922. Norman W. Krase, Virginia. 
Manufacture of urea from ammonia and carbon dioxide. 


382 DIGEST OF PATENTS 


Ammonium CARBAMATE (97 per cent) is heated at 150-165° in pressure vessel for 0.5-4 hours. 
A 40 per cent yield results and NH, is recovered. Water up to 10 per cent does not seriously 
interfere, 2.5-3 per cent aq. being beneficial. 


1,430,184—Sept. 26, 1922. — Raphael Pocius, Pennsylvania. 
Method of manufacture of phenols and the like. Fusion in stages without neutral- 
izing alkali. 

After the usual fusion of a sulfo comp. in NaOH to produce the PHENOL, sufficient water 
is added to dissolve organic sulfo deriv. while inorganic salts in large part settle to the bottom. 
Liquid containing sulfo acid and excess NaOH with some salt is decanted, conc., more NaOH 
added and again fused, process being repeated until sufficient quantity of desired product has 
accumulated. 


1,430,304—Sept. 26, 1922. Henry Dreyfus, England. 
Manufacture of acetic anhydride. 


Anhydrous sodium acetate (AcETIc acid, Na salt) is heated with excess sod. pyrosulfate, 
Na,S,O,, produced by strongly heating NaHSO,. Acetic anhydride may distil off as reaction 
proceeds. Preferably diluents such as glac. acetic or acetic anhyd. or mixtures thereof may be 
applied to bring about a more intimate contact of reacting salts. 


1,430,324—Sept. 26, 1922. Worth H. Ropresusu, Maryland. (U. S. Ind. Alc.) 
Process of making esters. Glycol acetate, etc. 

ETHYLENE dichloride and 1.5 parts fused potassium acetate are added to 1.5-2 parts of 95 
per cent alc. in closed vessel, and heated at 180° and 150 lbs. pressure for 1 hour. Solid 
products are sepd. and glycol acetate and alc. are frac. distilled. Other chlorinated hydrocarbons 
and other salts are claimed. 


1,430,585—Oct. 3, 1922. Alexander H. Ramact, Michigan. (Bostaph.) 
Process of producing aromatic hydrocarbons. Toluene. 

PHENOLS are converted into aromatic hydrocarbons by heating with H in excess at about 
700° in presence of a catalyst such as the lower oxide of iron. The OH group is converted to 
H. Side products are benzene, methane, phenol and aq. and varying conditions yield different 
amounts of these and of toluene. 


Note 1,365,849. 


1,431,394—Dec. 15, 1920. David F. Goutp, Pennsylvania. (Barrett.) 
Process of purifying naphthalene. Naphthalene in pure cryst. form. 

Molten crude NAPHTHALENE together with equal parts aq. is agitated and heated at 85° 
(above m.p. of naphthalene) until intimately mixed, then slowly cooled to 65° by reduction or 
addition of cold aq., centrifuged, etc. Crystalline laminated scales of uniform size and shape 
result. 


1,431,470—Oct. 10, 1922. Arthur Lapwortu, England. 
Manufacture and production of n-monoalkyl derivatives of aromatic com- 
pounds. Alkylation of amino compounds. 

Benzylidene 4-amino PHENOL or other and 5 parts benzene are refluxed at 100° and 0.73 
parts DIMETHYL sulfate added. After boiling 7.5 hours excess HCl is added and mixture steam 
distilled. Benzylidene product is hydrolyzed, benzene and benzaldehyde pass over, aq. soln. is 
conc. and bases freed by excess Na,CO,, Resulting 4-amino PHENOL (25-30 per cent) and methyl 
4-amino PHENOL (70-75 per cent) can be separated by HNO,, filtg. off nitroso methyl 2-amino 
phenol and reconverting nitroso and diazo derivs. to original comps. 


1,433,308—Oct. 24, 1922. John A. Srerrens, Maryland. (U. S. Ind. Alc.) 
Process of obtaining complete hydrolysis. Amyl acetate. 

Apparatus is shown whereby an ester, such as ETHYL acetate, in excess, and an alcohol, such 
as AMYL alcohol, may be continuously distilled as a constant boiling mixture of the ester and 
alcohol produced at a temp. lower than the b.p. of the original alcohol added, thus carrying the 
reaction beyond the point of equilibrium to completion. 


GROUP XXII.—INTERMEDIATES 383 


1,433,925—Oct. 31, 1922. 
Walter BapEr, England, and Donald A. Nicurinca.e, Maryland. 
Manufacture of aromatic derivatives. Alkyl sulfonamids. 


XYLENE sulfo chlorid, or other, is mixed with METHYL amin HCl or other alkylamin salt, 
and with Na,CO, or other neut. agent, together with 2-4 per cent aq. (not more than 5 per cent, 
while above 10 per cent hinders reaction) is heated at 80-100°. Product is extracted with 
benzene, etc. 


1,434,593—Nov. 7, 1922. 
Dominic J. Cutrown, Robert B. McCann and Don W. Bisseut, New York. (National.) 
Purification of pyrogallol. 


Crude PYROGALLOL is refluxed with 10 parts xYLENE or solvent naphtha (b.p. 140°), separated 
from impurities such as meta gallic acid and tar, cooled to cryst. dissolved pyrogallol, filt., etc. 
Solvent is reused. Or the crude is refluxed in an apparatus resembling that of Soxlet, etc. 


1,436,136—Nov. 21, 1922. Ernst ZERNER, Austria. 
Process of oxidizing liquid hydrocarbons. 


Crude gas oIL is extracted in closed vessel at 25° with a continuous current of liquefied 
SO, to remove unsaturated and other offensive hydrocarbons, remaining oil (about 40 per cent) 
is freed from SO, by distn. and air or oxygen blown through in presence of a basic substance 
such as slaked lime. 


1,436,214—WNov. 21, 1922. Gustav Trercuner, Austria. 


Process for oxidizing hydrocarbons and their oxidization products. (Product 
not claimed.) Fatty acids. 


Galician spindle o11 (sp. gr. 0.87) is treated with 0.5 parts fuming H,SO, (20 per cent SO,) 
for one-half hour at 60-80° to remove substances that tend to form resins, etc., and refined 
product is blown with air or other oxygen containing gas, at or above 110°, in presence of a 
catalyst such as zinc stearate, then the reactive portion is saponified. 


1,437,483—Dec. 5, 1922. Arthur A. Bacxuaus, Maryland. (U. S. Ind. Alc.) 


Apparatus for the production of aldehydes. Acetaldehyde or formaldehyde, etc., 
from corresponding alcohols. 


Apparatus is shown consisting of a hot water jacketed still to vaporize the aLcoHo, from 
whence vapors pass through a vaporizer and preheater that raise temp. to about 300° for ethyl 
ale. or 316° for methyl alc. then into a cylindrical iron reaction chamber containing a catalyst 
such as pumice stone, etc., carrying finely divided Cu, Ni, Cr or Fe (deposited by reduction of 
oxide with H) and then on to condensers to remove alc. and to scrubbers for aldehyde (acetic 
acid or aq.) Vaporizer, preheater and catalytic chamber may be enclosed in flues of a furnace. 


1,437,571—Dec. 5, 1922. Camille Vernet and Gabriel Raucu, Switzerland. (Grasselli.) 


Process of preparing sodium salts of anthraquinone alpha disulphonic 
acids. 


The sulfonation mixture containing mixed disulfo derivs. with beta comps. in small pro- 
portions, is added to 4 parts conc. sod. sulfate soln. After standing the 1.5 and 1.8-disulfo salts 
cryst. out free from the more soluble beta derivs. ‘The two alfa derivs. may then be sepd. by 
soly. in H,SO,. Or after sulfonation the 1.5 acid may be removed by diln., cooling, filtg., etc., 
and Na,SO, or NaHSO, soln. used to separate the 1.8 isomer from the residue. 


1,438,710—Dec. 12, 1922. Stuart P. Mituier, Pennsylvania. (Barrett.) 
Purification of naphthalene. 


Apparatus is shown and process described whereby crude NAPHTHALENE is distilled and 
vapors passed through 66° H,SO, at’ 134-144° or at such temps. without or preferably with re- 
duced pressure as will avoid condensation of vapors. Impurities are sulfonated and are retained 
while purified naphthalene vapors are carried further and condensed. 


1,439,128—Dec. 19, 1922. Walter Runce and Harry A. Curtis, New Jersey. (Bregeat.) 
Recovery of phenol vapors evolved from solvent recovery process, by phe- 
nolates. 
Apparatus is shown whereby vapors are passed through aq. soln. of sod. phenolate or 
cresylate to recover vapors of CRESOL or other phenol. In former patents crude cresol, etc., was 
employed as absorbent material. 


384 DIGEST OF PATENTS 


1,439,500—Dec. 19, 1922. George C. Bartty and Augustus E. Craver, New Jersey. (Barrett.) 
Catalytic oxidation of acenaphthene. Acenaphthenone. 


ACENAPHTHENE in vapor phase mixed with air (1: 6.2 parts) or other oxygen containing gas 


is heated at 400° with a catalyst such as vanadium oxide, or other metallic oxide. By-products 


are discussed in detail, with varying conditions that affect products of reaction. 


1,441,417—Jan. 9, 1923. David F. Goutp, Pennsylvania. (Barrett.) 
Purification of hydrocarbons. Purifying naphthalene, fluorene, acenaphthene, etc. 


The hydrocarbon is allowed to crystallize after treatment with H,SO, or other washing 
agent, impurities tending to separate on the surface of the crystals and are more readily re- 
moved by washing than by former liquid washing process. Crude separation of the bulk of 
the impurities may first be made before crystn. 


1,441,655—Jan. 9, 1923. 
James BappiLrty, Joseph B. PayMan and Harry WIGNALL, England. (British Dyes.) 
Manufacture of orthosulphonie acids of aromatic amines. 4-Toluidin 2-sulfo, 
2.4-xylidin 6-sulfo, or other ortho sulfo amins. 


An aromatic amin such as 4-TOLUIDIN, 2.4-XYLIDIN, etc., is refluxed with chlor sulfonic acid 
in presence of an inert solvent of high b. p. such as tetrachlorethane. 


1,442,491—Jan. 16, 1923. Joseph B. Marvin, Jr., New York. 
Method of chlorination.  1.4-Dichlor anthraquinone a-sulfo. 
ANTHRAQUINONE a-sulfo is first treated with 96 per cent H,SO, to react with chlorides present 


then sufficient oleum is added to raise to 23 per cent SO, and chlorine is admitted under 4 atms. 
pressure. Several methods of securing pressure are outlined. 


1,442,818—Jan. 23, 10923. Gilbert T. Morcan, England. (Imperial.) 
Manufacture of aromatic arylsulphonyl and arylene-disulphonyl deriva- 

tives of 1.4 naphthylenediamine and its sulphonic acids. 

1-NAPHTHYLAMIN and 1.5 parts TOLUENE 4-sulfo chloride are ground with a little more than 
I part anhyd. sod. acetate until pasty mass becomes solid and resulting toluene 4-sulfonyl 1- 
naphthylamin washed with aq. Na,CO, to remove unaltered toluene sulfo chloride then 6 parts 
purified deriv., in 13 parts 5N-NaOH and 30 parts aq., are coupled with 1.9 parts ANILIN that 
has been diazotized. The separated Na salt of azo comp. in 50 per cent alc. with a little NH,Cl 
is carefully reduced with Zn dust, filt., and amino deriv. pptd. by slight excess acetic acid. 


1,444,068—Feb. 6, 1923. Harry D. Giszs, New Jersey. (du Pont.) 
Process of manufacturing anthraquinone and phthalic anhydride. Anthra- 
quinone and phthalic anhydride from anthracene press cake. 

ANTHRACENE press cake containing 30-40 per cent anthracene and 20-30 per cent carbazole 
together with phenanthrene and other oils, mixed with NaOH, etc., in small excess of that re- 
quired to unite with and hold the carbazole, is vaporized continuously at 200—-300° and in current 
of air or oxygen, etc., mixture is carried into contact with a catalyst at 300-500° (preferably 
400°). The best catalyst is vanadic oxide but other oxides of V, and of Mo or Cr, etc., may 


be used. Alk. carbazole salt is removed from vaporizer and condensed phthalic anhyd. produced 


from phenanthrene is separated from crude anthraquinone by alk. carb. washing. 


1,445,162—Feb. 13, 1923. Herman W. Pautus, New York. (Royal.) 
Apparatus for converting formates into oxalates, 


Apparatus is shown and described whereby a formate .is subjected to a heat to render it 
plastic, then to further heat not greater than 220° to bring it to a molten condition, then sud- 
denly (2-3 secs.) raising the temp. to 360-440° by spreading liquid thinly over hot surfaces to 
remove a mol. of hydrogen without forming appreciable amounts of carbonate. 


1,445,544—Feb. 13, 1923. Theodor Opinca, Switzerland. (Lonza.) 
Process for the manufacture of crotonic acid from crotonaldehyde. 


Croton aldehyde is oxidized with oxygen in glac. acetic or other soln., using a manganic 
salt as catalyst. Method of preparing catalyst is given. 


at Abaca oo Rica ORE. Re end ee ee 


GROUP XXII.—INTERMEDIATES 385 


1,445,637—Feb. 20, 1923. Isador Mitier, New York. (Grosvenor.) 


Converting aromatic halogen substitution products into amines. Improved 
yields of amins from halogen compounds. 


Com’l. CuSO, 120 Ibs. in aq. soln. is converted to cuprammonium sulfate, Cu(NH,),SO,, 
by 1,040 lbs. 28 per cent ammonia and to this in an autoclave is added 450 lbs. 4-dichlor BENZENE, 
well ground, well agitated to obtain high dispersion, heated rapidly to 195-200° and maintained 
there for 14-16 hours during which time pressures will vary from 550-600 Ibs. (less than 1,000 
lbs.) down to 250 lbs. The copper should be 20 per cent or less of wt. of halogen comp. and 
ammonia 10-20 per cent in excess of theory. Yields are 100 per cent. Other halogen comps. are 
claimed. 


1,445,668—Feb. 20, 1923. Ira H. Dersy and William Hicsurc, Indiana. (Reilly.) 
Process of producing cresol, 


Crude tar acids or crude cCRESYLICc acid is treated with 5-:0 per cent of equivalent quantity 
of caustic alkali, grinding or heating until homogeneous. The caustic unites with impurities such 
as phenol, xylenol, sulfur comps., etc. The cooled mixture is diluted with equal parts of a 
solvent of b. p. less than 140° and o.5 parts aq. added to dissolve alk. salts. Water layer is 
removed and worked up for phenol and oily layer fractionated to remove solvent and collect part 
having b. p. 192—205° or pure cresol. 


1,445,870—Feb. 20, 1923. Robert M. Corr, Ohio. (Collins, 4.) 
Sublimating apparatus. 


Apparatus is shown consisting of a cylindrical vaporizing chamber with lengthwise heating 
element, a peripheral steam coil, horizontally inclined, and arranged to rotate, thereby causing 
crude material to travel axially around the periphery close to heating element with means for 
separating vapors by hot air blast at one end, and waste products at opposite end of chamber. 
Inclination of chamber may be varied. 


1,446,550—Feb. 27, 1923. Thurston N. Dissosway, New York. (Dissosway.) 
Process of removing impurities from resorcine. 


Tech. RESORCIN is ground, packed in percolator, covered with cold benzol and let stand a 
few hours, then soln. of impurities is allowed to flow off slowly while replacing the benzol as it 
falls below the level of the material, until a bulk equal to the original benzol has been added. 
Impurities such as phenol and catechol are recovered. 


1,446,551—Feb. 27, 1923. Thurston N. Dissosway, New York. (Dissosway.) 
Process of purifying resorcin. 


Tech. RESORCIN is partly purified by extraction with limited amount of aq. at 90° or of 
benzol in a percolator as in 1,446,550, and crystals obtained are sublimed at temp. of 115-135°, 
or low enough to avoid decompn. of resorcin. Apparatus for sublimation is shown. 


1,446,564—Feb. 27, 1923. Louis L. Jackson, New York. (Dissosway.) 
Sublimation apparatus. Apparatus for subliming resorcinol. 


Apparatus is shown comprising a heating chamber, in continuation of and in direct con- 
nection with a condensing chamber, a conduit connecting the outside ends of two chambers, 
means (fans) for causing vapors to circulate at determined rate continuously from heating cham- 
ber to condensing chamber and return. Heating chamber increases in diameter toward con- 
densing chamber, heating pans are supported out of contact with heated metallic surface, so that 
vapors may circulate freely, and accessory devices. 


1,447,557—Mar. 6, 1923. David A. Lecc, England. (Adam.) 
Reduction of nitrocompounds. 

A nitro comp. such as NITROBENZENE is passed in a state of vapor.together with a reducing 
gas such as H, or the vapor of a body capable of being dehydrogenated such as alcohol, over a 
catalyst prepared by fusing cupric oxide, and breaking up the fused material into pieces. Heat 
is applied at first and temp. is maintained by heat of reaction supplemented by small amount of 
outside heat. 


1,448,688—Mar. 13, 1923. David F. Gourp, Pennsylvania. (Barrett.) 


Naphthalene erystals and process of making the same. A new form of naph- 
thalene crystals, less bulky and sticky when in storage or packages. 


git ll 


386 DIGEST OF PATENTS 


A mixture of NAPHTHALENE and aq. or aq. salt is violently agitated at 85° until an intimate 
mixture results, then is cooled slowly to 65° at rate of 3° per hour, while slowly agitating. 
Crysts. are laminated like fish scales, and are clear and transparent, much thicker than usual 
forms of crysts. 


1,449,121—Mar. 20, 1923. Ralph H. McKer, New York. 
Process of producing carvacrol and thymol. 


Spruce turpentine is purified by steam distn. to remove SO, and tarry bodies until 80-90 per 
cent of the oil is in distillate, which is dried with CaCl, or by distilling off about 2 per cent, and 
treated with about its own volume of fuming H,SO, (20 per cent SO,) at 25-30° or at least be- 
low 50°. Resulting soln. containing 1.2.4 and 1.3.4 sulfo acids is neut. by CaCO, and Ca salts 
of sulfo acids in filtrate, recovered as Na salts, are fused in alkali. Carvacrol 80-85 per cent 
and thymol 15-20 per cent are sepd. by distn. Other recovery methods are outlined. 


1,449,423—Mar. 27, 1923. Alexander Lowy and Arthur M. Howatp, Pennsylvania. 
Production of naphthyl amines. Naphthylamins from naphthols. 


Vapors of 2-NAPHTHOL or other and NH, are passed through a hot reaction zone containing 
an oxide of Al at temp. of 300—550° to produce 2-naphthylamin. Other derivs. claimed. 


1,449,918—Mar. 27, 1923. Frederick W. Sxrrrow and James Dick, Canada. (Shawinigan.) 


Process for the production of diesters from vinyl esters. Ethylidene diacetate 
or other. 


Glac. acETIc acid, too lbs. and 5 lbs. HgO are heated to 70-80°, then 2 lbs. 70 per cent oleum 
added to ppt. active mercury sulfate, and to this is slowly added 143 lbs. of vinyL acetate, keeping 
temp. at 80-90°. After 2 hours a go per cent yield of ETHYLIDENE diacetate is obtained. Ex- 
cess sod. acetate is added to neut. H,SO, and product is distilled. Oxides of sulfur without Hg 
may act as catalysts and other diesters of dihydroxy alcohols are claimed. 


1,450,569—Apr. 3, 1923. 
Robert R. Wri.iaMs, Illinois, and Herbert IL. J. Hatter, Ohio. (Hunt.) 


Apparatus for producing ketones. 


Apparatus is shown for converting secondary ALCOHOLS to ketones, the reaction chamber 
consisting of a coil of copper-zinc wire gauze around a centrally located pipe through which 
vapors of alcohol and air enter at 50° or other determined temp. from a preheater, heated by 
exit vapors from reaction chamber. A suitably placed asbestos gasket acts as heat insulator be- 
tween the two chambers. External heat is applied to start reaction which is exothermic and 
with regulation of size and arrangement of apparatus, quality of alcohol, its rate of admission, 
etc., operation will continue indefinitely without further externai heat. 


1,450,982—Apr. 10, 1923. 
Melville J. Marsuatt and George S. SHaw, Canada. (Shawinigan.) 
Process of removing destructive substances from nonaqueous media. Re- 
moval of mineral acids, etc., in manufacture or purification of esters. 

ETHYLIDENE diacetate made by passing ACETYLENE gas into glac. ACETIC acid at 70-80° using 
preferably HgSO, as catalyst, is first sedimented and solid products removed then anhyd. sod. 
acetate is added and resulting Na,SO, ppt. removed, leaving a mixture of acetic acid (20-30 per ; 
cent) and ethylidene diacetate (70-80 per cent), etc., free of H,SO, which may be distilled with 7 
but slight decompn. To acetal from acetylene and alcohol with catalyst, is added sodium ethylate, a 
and for other easily hydrolyzed esters suitable anhydrous agents inactive and insol. in the Z 
ester may be employed. 7 


1,450,990—Apr. 10, 1923. Edmund C. Suortry, District of Columbia. 
Process of making 2-naphthol 3-carboxylie acid. Improved yields of 2-naphthol 
3-carbo acid. 


The usual process for converting sod. 2-NAPHTHOL to the carbo. deriv. by heating under 
pressure with CO, is followed, using pressures of 50 lbs. and temp. of 200-250°, and providing 
a continuous current of CO, into the apparatus and an outgoing current of excess CO, carrying 
2-naphthol, the presence of which in the reaction mixture is one cause for poor yields. 


1,451,357—Apr. 10, 1923. Thomas B. Aupricu, Michigan. (Parke, Davis.) 
Nitrobenzoic acid esters of trihalogentertiary butyl alcohol. 


GROUP XXII.—INTERMEDIATES 387 


Tertiary Buty. alcohol is refluxed at 100° with equal parts 3-nitro BENzoyy chloride. Other 
halogen and isomeric nitro benzoyl derivs. are claimed. 


1,451,489—April 10, 1923. Oliver W. Brown and Clyde O. Henxez, Indiana. 


Process for the manufacture of azoxy, azo, hydrazo, and amino compounds. 
Reduction of nitrobenzene with Pb, Bi or Tl as catalysts. 


NITROBENZENE and excess hydrogen, which need not be pure, are passed at 200-360° over a 
catalyst of finely divided lead, bismuth or thallium prepared from the oxide, hydroxide or 
carbonate, etc., of the metal reduced in a current of H gas. For bismuth the nitrate is pptd. 
by NH,OH, ppt. dried and reduced in current of H at 250-300°. Varying proportions of anilin, 
azo benzene, azoxy and hydrazo benzene are obtained, mainly the first two, higher temps. 
yielding more anilin. 


1,451,666—Apr. 10, 1923. Stuart P. Mintzer, Pennsylvania. (Barrett.) 
Production of alpha-naphthylamine. Improved process for 1-naphthylamin. 

NAPHTHALENE is nitrated to alfa nitro deriv. and reduced with Fe and an acid in usual way, 
then instead of distilling off the 1-naphthylamin from the residual FeO and Fe, etc., it is ex- 
tracted by equal parts refined solvent naphtha at 60°, filt. or centrifuged, etc., then steam dis- 
tilled to remove the solvent. 


1,452,481—Apr. 17, 1923. 
James BappiLEy, Joseph B. Payman and Ernest G. Barnsripce, England. (British Dyes.) 
Manufacture of 1l-naphthol 4-sulphonie acid. 
1-NAPHTHOL is dissolved in 4 parts tetra chlor ethane or other inert solvent cooled below 
10°, equimol chlor. sulfonic acid run in, temp. kept at 50° for 24 hours, cooled, diluted, neut. 
with Na,CO, solvent separated from soln. of 1-naphthol 4-sulfo acid, which is conc. etc. Or- 
ganic impurities are pptd. by adding BaCl, to soln. after removal of organic solvent. 


1,452,520—Apr. 24, 1923. Waldemar O. Mitscuertine, Delaware. (Atlas.) 
Process for carrying out continuous fusions, 


Apparatus is shown whereby the material in form of a soln. is passed continuously through 
a rapidly rotating tube which is externally heated to a point to effect fusion. — 


1,452,774—Apr. 24, 1923. Frederick W. Atracx, England, and Charles W. Soutar, Scotland. 


Intermediates and dyestuffs of the anthraquinone series. (Process also claimed.) 
3-Chlor 2-amino anthraquinone, m.p. 221°. 
2-Amino ANTHRAQUINONE in glac. acetic suspension is treated with Cl until desired increase in 
weight, then boiled 30 m. to crystn. of orange yellow needles. Other diluents such as nitro- 
benzene with or without Na,CO, or other neutralizing agent may be used. 


1,452,774—Apr. 24, 1923. Frederick W. Atack, England, and Charles W. Sourar, Scotland. 
Intermediates and dyestuffs of the anthraquinone series. (Process also claimed.) 
2-Amino 1-brom 3-chlor anthraquinone. 
2-Amino 3-chlor ANTHRAQUINONE with 0.5 parts N,CO, in 9 parts nitrobenzene suspension are 
treated with about 1 part Br. also in nitrobenzene (3 parts), adding the Br. at usual temp. over 
period of 20 m., then warming at 60° for 1.25 hours. 


1,453,215—Apr. 24, 1923. 
Clyde IL. Voress, New York, and Vernon C. Canter, Pennsylvania. (Gasoline Rec.) 
Volatilizing and distilling absorbed wapors. Separating benzol, toluol, etc., and 
naphtha. vapors continuously from absorbent. 


Apparatus is shown whereby vapors evolved in distn. of coal, etc., are absorbed alternately 
in two towers of activated charcoal. When upwards of 20 per cent by wt. of vapors are ab- 
sorbed in one tower shift is made, steam is introduced to displace most of the vapors, and con- 
densed steam and other vapors cooled and separated. Current of vapors from still are again 
turned into the first tower to displace condensed steam and cool charcoal, then heavier vapors are 
passed to displace lighter ones. By alternate use of two towers process is continuous. 


1,453,659—May 1, 1923. 
Guillaume de Montmo.uin, Josef Srreter and Gerald Bonuore, Switzerland. (Basle.) 
Intermediate product for the manufacture of dyestuffs and process of mak- 
ing same. 4.4'-Dioxy 3.3/-dicarbo 1.1/-dinaphthyl ketone and 1-naphthol 2.4-dicarbo. 


388 DIGEST OF PATENTS 


Filtrate obtained in 1,387,596 by treating 1-NAPHTHOL 2-carbo in alk.-alc. soln. with CCl, and 
filtering off the dye, is acidified with HCl, filt., ppt. dissolved in dil. NaOH and salted out, gives 
4.4/-dioxy 3.3’-dicarbo 1.1/-dinaphthyl ketone. Filtrate from latter pptn. is made acid, filt., ppt. 
extracted with boiling Ba(OH), water, soln. filt. and pptd. by acid gives 1-naphthol 2.4-dicarbo. 
If original soln. was aqueous the operations are changed in order, first the ketone, then dye, and 
finally the dicarbo deriv. being separated. Relative proportions of products may be altered by 
varying conditions. 


1,453,766—May 1, 1923. Elmer H. Payne and Samuel A. Montcomenry, Illinois. (Standard.) 


Catalyst and method of making the same. Catalyst for chlorination of hydrocarbons 
such as methane. 


Apparatus is shown for passing Cl through a hydrocarbon material at 150° until a coal- 
like porous solid mass is formed and HCl is no longer formed, then METHANE or other hydro- 
carbon gas and 3 parts Cl are passed through this as catalyst then through tubing subjected to 
light rays from a mercury vapor arc for further chlorination. Analysis shows that catalyst con- 
tains none but combined Cl. 


1,454,204—May 8, 10923. Alois Z1inkE, Austria. (Pereira.) 
Process of manufacturing dioxyperylene and perylene. 

Dioxy PERYLENE mixed with 4 parts Zn. dust is heated over zinc coated pumice in current of 
H gas at temp. above b.p. of perylene, 480—-500°, whereby perylene is distilled off. Reaction is 


almost quantitative. The metal may or may not act as catalyst. 
Note 1,454,205. 


1,454,205—May 8, 1923. Alois Zinxe, Austria. 
Process of manufacturing dioxyperylene. (Product also claimed.) 

2.2/-Dimethoxy 1.1/-DINAPHTHYL mixed with 4 parts AICI, is heated dry below m.p. of dioxy 
perylene, 140-150°, for 2 hours. Mass is lixiviated with dil. HCl and solid dioxy perylene 
sepd. by filtn. in vacuum. Other alkyl derivs. of dioxy dinaphthyls are claimed. 

Note 1,454,204. 


1,454,462—May 8, 1923. Arthur A. Bacxuaus, Maryland. (U. S. Ind. Alc.) 
Process of producing high-grade esters. Esters of high purity, especially ethyl 
acetate. 


Apparatus is shown whereby ALCOHOL, ACETIC acid and a catalyst are intermingled, rectified 
as a constant boiling mixture, diluted with aq. to form two layers, re-rectifying the layer con- 
taining high percentage of ester and returning aq. layers to still. An ester of 95-100 per cent 
strength is produced. 


1,454,463—May 8, 1023. Arthur A, Backuaus, Maryland. (U. S. Ind. Alc.) 
Process of esterification. Ethyl acetate, free from alcohol, and other esters. 


Apparatus is shown in which an alcohol, an organic acid and a catalyst are caused to react 
in a column while continuously removing some of the ester as formed and continuously feeding 
to the reaction mixture fresh quantities of materials, the reaction being subjected to a current 
of vapors evolved from reacting materials by an arrangement of alternating storage cups and 
liquid contact cups. 


1,455,448—May 15, 1923. Gustav Prrers, Germany. 


Process of manufacture of diphenylenediketones from anthracene com- 
pounds. Anthraquinone, etc. 


ANTHRACENE or deriv. such as oxanthrol, mono or dichlor anthracene, etc., in 5-10 parts 
conc. acetic acid at 80-90° is mixed with a small proportion of fuming HNO, and oxygen in- 
troduced under pressure. Cobalt nitrate and nitrous gases or other oxygen carrier as catalyst 
and propionic or other aliphatic acid may be used as solvent with some indifferent non-acid 
diluents. 


1,456,848—May 20, 1923. Harry D. Grsss, California. (U. S. Govt.) 
Process for purifying anthracene press cake. 


ANTHRACENE press cake mixed with 5 per cent NaOH is heated in closed iron vessel to 246° 
and a current of air is passed at 3 cu. ft. min. for each sq. ft. of screen surface in first com- 
partment of condenser. Condenser consists of a series of compartments, separated by screens 


GROUP XXII.—INTERMEDIATES 389 


of wire cloth of 0.5 in. mesh. Temp. of first compartment is 150—250°, preferably 200°, Alkali 
need not be added to press cake, especially in large scale operations. Several treatments of ma- 
terial may be advisable. Fractions collect in order of carbazole, anthracene, phenanthrene for 
three compartments, (when carbazole is not held back by alkali). 


1,456,969—May 29, 1923. Oliver W. Brown and Clyde O. Henxez, Indiana. 


Process for the manufacture of aromatic amino compounds. Amino from nitro 
compounds with larger yield and greater purity. 


ANILIN is produced when NITROBENZENE or other nitro comp., as-vapor is mixed with excess 
H and passed at 230° over a catalyst consisting of finely divided tin and tin oxide (prepared 


‘by reducing tin oxide in a current of H). Temp. range is 200-350° and other catalysts such as 


Co, Cu, Fe, Pt, Os, Ir, may be used. Preparation of catalyst is described. 


1,457,543—June 5, 1923. Stuart P. MitztER and John R. Hess, Pennsylvania. (Barrett.) 
Nitrating aromatic hydrocarbon. Nitrating solid hydrocarbons by simplified process. 


Solid hydrocarbons such as NAPHTHALENE in molten condition are run at regulated rate into 
55 per cent H,SO, at 40° with violent agitation, whereby it is granulated and in condition to be 
readily nitrated. HNO, (40°) is gradually added at 40-45°. Previous handling and pulverizing 
of solid material before nitration is saved. 


1,458,491—June 12, 1923. Ralph H. McKee and Hermon C. Coorrer, New York. (McKee.) 


Method of making oxidized aromatic substances. Benzoic acid or other oxidized 
aromatic acid. 


Apparatus is shown wherein an excess of TOLUENE, or other, may be oxidized with 7-8 vols. 
chromic acid (1 part Na,Cr,O,, 6 parts aq. and 6 parts 66° H,SO,) keeping at temp. of 85°, 
excess toluene dissolving and removing benzoic acids as formed, and preventing decompn. Ag. 
and toluene soln. are sepd. by decantation and benzoic acid pptd. from toluene portion by alk. 
carb. 


1,458,715—June 12, 1923. Ellis A. LLuoyp and Victor P. GersHon, New York. (Grosvenor.) 
Process for making nitrobenzoic acid and intermediates. 


2-Nitro TOLUENE, com’l grade, is refluxed with 0.14 parts 65 per cent HNO, (1.4) for 4 days, 
while 2 parts 90-95 per cent HNO, are slowly added to maintain the effective strength of the 
acid. Nitric and nitrous acids are recovered. The sepd. and washed benzoic acid crysts. are 
converted to Na salt and reduced in aq. soln. by purified Na,S to 2-amino benzoic or an- 
thranilic acid. 


1,459,081—June 10, 1923. Pierre A. Barset, France. 
Process of continuous sulphonation of benzene, applicable to impure 
benzenes,. 


Apparatus is shown wherein impure petroleum BENZENE (50-55 per cent C,H,) is sulfonated 
continuously in vapor phase, with fuming H,SO, in a distilling column on the counter current 
principle, introducing benzene vapors at the bottom of the tower where they bubble up through 
successive heating plates at boiling temp. of hydrocarbon, unsulfonated non-benzene vapors 
passing out at the top, and sulfuric liquid with benzeno sulfo acid flowing out at the bottom. 


1,460,708—July 3, 1923. _ ‘William M. Deun, Washington. 
Process of manufacturing diazodinitrophenol. 


Fuming HNO, (1.5) in a converter is covered with layer of 2 parts neut. paraffin oil, wax, 
etc., and 0.4 parts ammonium salt of PICRAMIc acid with o.1 parts alc. or carbohydrate material, 
as wood or sugar, etc., are added to the HNO,, keeping temp. so that minimum nitrous fumes 
escape, then heated gradually to 100° until gas no longer passes off. The paraffin layer is run 
off and reused, and diazo comp. pptd. as yellow powd. by running acid liquid in thin streams 
into water well agitated. 


1,460,774—July 3, 1923. Andre Want and Robert Lantz, France. (St. Denis.) 
Manufacture of 2-oxy l-aryl naphthylamines (Product also claimed.) 1-Phenyl 
i-amino 2-naphthol, or other. 


1-Chlor 2-NAPHTHOL and 5 parts ANILIN are refluxed 3-4 hours until HCI ceases to evolve, 
then excess reagents are removed by steam distn. Other 1-halogen 2-naphthols and other aryl 
amins are claimed. 


390 DIGEST OF PATENTS 


1,461,745—July 17, 1923. Frederick W. Atacx, West Virginia. 


Process of purifying anthraquinone and its derivatives. A special solvent for 


purifying anthraquinone. 


Crude ANTHRAQUINONE, dry or paste, is heated with 3.3 parts PHENOL, monohydrate until 
temp. is 105°, centrifuged to remove mineral matter and cooled to 10-25° to crystn. Mother 
liquor may be used several times before it needs re-distn. 


1,463,190—July 31, 1923. Edwin O. Barstow, Michigan. (Dow.) 
Method of making benzoic acid and salts thereof. Increased yields in benzoic 
acid mfr. 


BENnzyt chloride and bleaching powd. together with lime and aq. are heated to 95° in pres- 
sure vessel when exothermic action begins and is maintained by its own heat, 3-4 mins. being 
sufficient. No raw material is lost and foaming avoided, time is saved, and yields increased. 


1,463,255—July 31, 1923. 
George O. CurmeE, Jr., and Herman B. Heyn, Pennsylvania. (Union Carbide.) 
Process of preparation of benzoates and benzoie acid from dibenzyl. 


Apparatus is shown wherein DIBENZYL with 0.4 parts MnO, or other Fe, etc., comp. as 
oxygen carrier, and 4 parts NaOH containing less than 10 per cent aq. are heated to 200—-300° 
under pressure and oxygen or oxygen containing gas mixture passed over reaction mixture until 
no more dibenzyl remains. Caustic must be in excess of that required to neut. benzoic acid 
formed. Product is Cl free. 


1,464,844—Aug. 14, 1923. Charles R. Downs, New Jersey. (Barrett.) 
Sublimation process. Fractionation by sublimation. 


Apparatus is shown whereby impure ANTHRAQUINONE or PHTHALIC anhyd. or other poly- 
nuclear aromatic hydrocarbon and oxidation product of same together with a hot neutral gas 
are passed into a cooling zone where one substance is crystd. and sepd. and the remaining in- 
gredients of the mixture are subsequently passed into successive stages or cooling zones, where 
they are maintained for considerable time at definite temps. such as 200° for anthraquinone, etc. 


1,465,689—Aug. 21, 1923. David SEGALLER and David H. Peacock, England. (British Dyes.) 


Manufacture of oxy and sulpho-oxy derivatives of anthraquinone. Anthra- 
quinone derivatives from phthalic anhydride, etc. 


PutTuatic anhyd. and equimol PHENOL 4-sulfo, or disulfo or other phenol not exceeding 108 
MM., with about 0.5 parts boric acid are heated at 180-200° in 5 parts 96 per cent H,SO, to pro- 
duce ANTHRAQUINONE 1-oxy 4-sulfo or disulfo which when sepd. and heated to 240-250° in 10 
parts H,SO, for 3 ‘hours, cooled, etc., yields quinizarin or purpurin. Or sulfo acid without iso- 
lation can be heated at 250° with or without more H,SO, and with HgO as catalyst. 


1,466,411—Aug. 28, 1923. William A. Peters, Jr., Delaware. (du Pont.) 


Distillation apparatus. Condensing materials of high b.p. with freezing points close to 

b.p., such as camphor (205° and 176°). 

Apparatus is shown consisting of a still and upright condenser or shell, with bottom adapted 
as condensate collector and with cooling pipe crosswise of chamber lying directly in path of 
vapors so that condensate may fall to bottom, and connecting with a condenser arranged so 
that vapors from still can maintain condensate on said bottom in liquid phase, with means for 
withdrawing this liquid condensate. 


1,466,6853—Sept. 4, 1923. Arthur Uuuiricu, Germany. 


Process of manufacture of diphenylene diketones as anthraquinone or its 
derivatives. Anthraquinone or other diphenylene diketones and sulfo acids, from an- 
thracene, chlor. or sulfo anthracene, oxanthranol, etc. 

ANTHRACENE (95 per cent) is heated in closed vessel to 90° with 5 parts anhyd. acetic acid 
and 0.6 parts acetic anhyd. then o0.5-1 per cent NaNO, added and oxygen introduced under 
pressure. Solvent can be distilled and reused. Other anhydrous acids and anhydrides or 
anhydrous salts to remove aq., with neutral solvents such as benzene or dichlor benzene and 
catalysts such as MnO, or BaO, are claimed. 


GROUP XXII.—INTERMEDIATES 391 


1,466,991—Sept. 4, 1923. Paul Corrrincer, Michigan. (Dow.) 
Process for making phenol. 


BENZENE is sulfonated, mixture neut. by CaCO, or CaSO,, and Ca benzene sulfo con- 
verted to Na salt, which is sepd., dried, and with 4-7 equivalents Ca(OH), is heated in drum 
to 425-500° for short time, then current of steam and SO, or CO, forced in at temp. to maintain 
steam as vapor. Phenol is distilled off, sepd. by gravity, purified and condensed to U. S. P. 
strength. 


1,467,258—Sept. 4, 1923. Arthur Uniricu, Germany. 


Process of manufacture of diphenylene diketones as anthraquinone or its 
derivatives. Anthraquinone, etc. 


Process is similar to 1,466,683 using organic acids that may contain aq. with fuming HNO, 
or nitric oxides and metal nitrites which react with the organic acid to form organic salts that 
react with HNO, produced, forming metal nitrates, preferably using sufficient organic metal 
salt to transform all HNO, into metal nitrate. 


1,467,711—Sept. 11, 1923. ; Guillaume de MontMo.uin, Switzerland. (Basle.) 
Process for the manufacture of intermediate products and new dyestufts 
derived from diarylsulphones. (Product, not process, claimed.) 2-Amino 4-acetyl 
amino 4/-methyl 5/-sulfo diphenyl sulfone, or other. 
TOLUENE 4-sulfinic acid is condensed with 2.4 dimitro chlor BENZENE, sulfonated, reduced and 
acetylated before diazotizing to form azo dyes. 
Note 1,359,969. 


1,467,905—Sept. 11, 1923. Thomas Mipci&y, Jr., Ohio. (Gen. Motors.) 
Hydrogenation furnace. Hydrogenation, especially of unsaturated hydrocarbons, for fuels. 

Apparatus consists of a reaction chamber, adapted to high pressures, for catalytic material, 
with heating jacket in a plurality of units to control heat applied and heat lost by radiation, 
with means for heat insulation and measurement of temp. at any part of chamber, with condenser 
and recirculating pipe, with second condenser surrounding its upper end so that condensate will 
return to chamber. Operation of apparatus is described. 


1,468,220—Sept. 18, 1923. Clinton P. TownsgEnp, District of Columbia. (Hooker.) 
Producing organic chlorine substitution products. Recovery of by-products in 
chlorination of benzene or other organic body. 
Mixed BENZENE and chlorinated hydrocarbon vapors escaping with HCl from chlorination 
vessel are passed into an aq. liquid containing a reactive metal oxide such as ZnO or MnO, in 
suspension. 


1,469,586—Oct. 2, 1923. Ralph A. Neztson, New York. (National.) 
Production of hydrazanisol. Improved process for hydrazanisol. 

HyprazANisor is produced in crystals of size that may be sieved from zinc residues. Thirty 
parts 2-nitro ANISOL, 27 parts denatured alc. and 5 parts NaOH (35-43° Bé.) are refluxed and 
40 parts Zn dust added gradually for several hours. Refluxing is continued until mass is 
light gray. Mass is then very slowly cooled with agitator so as to produce crystals of suf- 
ficient size, diluted, filt. and washed on a 100 mesh screen to remove zinc residues. 


1,470,039—Oct. 9, 1923. Roger N. Watiacu, New York. (Grasselli.) 
Process of making 2-3 oxy-naphthoie acid. Making 2-oxy 3-naphthoic acid with 
less 2.1 isomer as impurity. 

In pressure vessel 1 part anhyd. 2-NAPHTHOL, Na salt, is dissolved in 0.45 parts 2-NAPHTHOL 
at 225°, CO, pumped in at pressure of 200-300 lbs. and temp. of 225-250° maintained for 1 hour. 
By this process the concentration of aq. formed by secondary reaction is kept lower by diluent 
effect of solvent and production of 2-oxy i-naphthoic acid and decomposition products such as 
naphthoxanthrone is much lower. Variations of process are claimed. 


1,472,791—Nov. 6, 1923. William M. Deun, Washington. 
Process of manufacturing ammonium picramate. Ammonium picramate made by 
cheaper process in higher yields and greater purity. 


Finely divided picric acid 100 parts in closed vessel are partly neutralized with aq. con- 
taining 7.5 parts NH,, 670 parts 10 per cent NH,SH slowly added and well mixed at 40°, while 


392 DIGEST OF PATENTS 


preventing escape of NH, and access of O. Ammonia is recovered and reused. A 90 per cent 
yield of pure mono amino deriv. is claimed. 


1,474,507—Nov. 20, 1923. Arthur E. Barnarp, Delaware. (du Pont.) 
Process of recovering residual anthraquinone from a sulphonation mass. 


After sulfonating ANTHRAQUINONE with equal parts oleum (30 per cent) about 4 per cent aq. 
is added during 20 m. to destroy free SO,, charge removed to crystallizing tank and water 
added as follows: during each successive 30 m. periods 5 per cent aq., 5.25 per cent aq., 6 per 
cent aq., and 14.3 per cent aq., thus reducing acid strength to 95 per cent, 90 per cent, and 
75 per cent, keeping temp. at 110°. MLarge crystals of anthraquinone of higher purity than 
original material result. Advantages of process given in detail. 


1,474,928—Nov. 20, 1923. Guillaume de MonrMo.uin and Josef Sp1eLEeR, Switzerland. (Basle.) 


Carbonyl derivatives of alpha naphthol and process of making same. Esters 
of 1-naphthol 4-carbo acid or the 2.4-dicarbo deriv. 


One mol. I-NAPHTHOL in 3-4 parts 40 per cent NaOH and 8 parts methyl alc. is mixed 
with 1 mol. carBoNn tetrachloride and 0.007 part copper powd. and temp. kept below 50° for 
several hours. Soln. is neut. with mineral acid, the methyl ester of 1-NAPTHOL 2.4-dicarbo acid 
that is pptd. is removed, methyl alc. distilled from liquid and methyl ester of 1-naphthol 4-carbo 
acid pptd. by acid. 

Note 1,387,596. 


1,477,058—Dec. 11, 1923. Arthur E. Houteuan, Delaware. (du Pont.) 


Process for the preparation of catalytic compounds and the product ob- 
tained thereby. Aluminum chloride in new form as catalyst for transforming higher 
to lower boiling point hydrocarbons. 

Metallic Al is first prepared in thin sheets by dropping molten metal on a highly polished 
revolving plate. The Al sheets are then placed in reaction vessel, covered with layer of a 
liquid hydrocarbon o1L, such as 3-xYLENE, and a stream of dry HCl vapor introduced by pipe 
extending to bottom of vessel. The AICI, formed combines with hydrocarbon to a catalytic comp. 
which settles to bottom of vessel as a dark BrR immiscible layer. All of the Al should be con- 
verted to chloride. Comp. can be prepared in large quantity and handled and stored conveniently. 


1,477,829—Dec. 18, 1923. Ernest M. Jouansen, Pennsylvania. (Atlantic.) 


Sulpho compound and its production. 

Non-oily crystalline or crystallizable bodies derived from the high boiling point distillate 
from destructive distillaton of mixed o11, diluted with lighter oil, are sulfonated in usual manner 
until soluble in warm aq. and sulfo acids separated after dilution and neutralization. 


Group XXIII—APPLICATIONS, BY DYE GROUPS AND IN GENERAL. 


This group of abstracts includes methods of applying dyes to the fiber, as well as the prep- 
aration of dye mixtures, compounds and lakes. When a new dye is claimed in the form of its 
application, however, it is classed among dye patents, not in this group. 

The abstracts are distributed into two main classes of general and of special applications. 
Processes may apply in general to any coal tar dye, or they may be special methods for a cer- 
tain dye group. Distribution has been made therefore into applications of general use for coal 
tar dyes, and a number of subgroups of special applications to certain dye groups, and such dis- 
tribution is indicated by letters in parentheses which appear in indexes and abstracts as follows: 


General applications: Without symbol. 
Special applications: 
Subgroup II.—Anilin Black. Symbol (Ab). 


Subgroup ITI.—Anthraquinone. (An). 
Subgroup V.—Azin, Indulin. (AI). 
Subgroup V1I.—Azo. (Az). 
Subgroup VII.—Indigo. (In). 
Subgroup IX.—Nitro. (Nt). 
Subgroup X.—wNitroso. (Ni). 
Subgroup XI.—Oxazin. (OX): 
Subgroup XIII.—Quinolin. (Ou). 
Subgroup XV.—Sulfur. (Su). 
Subgroup XVIII.—Triphenylmethane. (Tr), 


Subgroup XIX.—Xanthone. (Xa). 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL, 393 
SUBGROUP II.—ANILIN BLACK. (Ab.) 


90,417—May 25, 1860. John ZENGELER, Illinois. 
Improved ink-powder and dye from anilin colors. (Process, not product, 
claimed.) Anilin black ink powder. 


Dextrin 128 parts, anilin salt 32 parts, CuSO, 14 parts, KC1O, 8 parts, NH,Cl 32 parts, and 
K,Cr,O, 4 parts, are powdered and mixed together. Other components and proportions claimed. 


106,616—Aug. 23, 1870. Robert Pinkney, England. 
Improvement in the production of colors for dyes, ink, etc., from anilin. 


ANILIN salt 320 parts, nickel salt 20 parts, NaClO, 60 parts, and water 640 parts, are 
applied together or separately to fabrics. 


109,025—Nov. 8, 1870. Jean Lampert, New York. (G. Bourgade.) 


Improvement in removing dyes made from anilin, etc., from portions of 
fabrics. Discharging anilin dyes white. 


Powdered zinc, tin, or other, mixed with powdered gum or other adhesive, are printed on 
fabric dyed with anilin black, let dry, then washed. In place of metals, alkali cyanides may 
be used with rosanilins, for instance, to produce white cyano rosanilins. 


127,102—May 21, 1872. Robert Pinkney, England. 


Improvement in the manufacture of dyes from anilin. Dyeing anilin black, etc., 
by aid of salts of vanadium and uranium, etc., instead of copper. 


Anitin HCl, 150 parts, vanadium salt 0.125 part, or uranium salt 5 parts, nickel chloride 
20 parts, and KCIO, (NH, deriv.) 100 parts with 2500 parts aq. are used as dye mixture to 
be applied to fiber. Methods for dyeing and printing are described. 


134,066—Dec. 17, 1872. 5 
Leon Jarosson, France, and Jean J. Mutier Pack, Switzerland. (Brown.) 


Improvement in dyeing black with anilin colors. Improved method of fixing 
or aging fibers dyed with anilin black, naphthylamin chocolates, etc. 


Fabric is mordanted with FeCl, and dyed in bath of anit1n HCI containing chlorate then 
heated slowly to 50° for 3-5 hours in rotating iron cylinder, allowed to remain in heap for 
several hours, passed through weak acid bichromate bath at 50°, soaped, etc. 


213,907—Apr. 1, 1879. Henri Kinspourc, France. (Eddystone.) 


Improvement in processes of dyeing aniline-black. Dyeing vegetable fibers black 
at low temps. by one bath process, uniformly and cheaply. 


Fabric is immersed in bath at 10-15° containing bichromate, sulfuric acid and anizin HCl. 
The color is thus formed directly on the fiber without pptn. in dye bath. 


248,934—Nov. 1, 1881. Jules J. Lenore, France. (Posselt.) 
Dyeing aniline-black upon cotton. Improved method of applying anilin-black. 


Fabric while passing over rollers in special form of apparatus described, is showered from 
above by spray of anilin soln. containing FeCl,, anizin oil, HCl, chlorate, CuSO,, etc., aged 
and again showered with bichromate-HCl soln. Drawings and description of apparatus given. 


283,220—Aug. 14, 1883. Alexander N. Dusors, Pennsylvania. 
Dyeing aniline-black. Dyeing anilin black on vegetable fiber cheaply and quickly. 


Fabric dyed in bath of tepid water containing ANILIN salt, acid, sulfate of soda, and bi- 
chromate and moved about for 40-50 minutes. 


287,112—Oct. 23, 1883. Alexander N. Dusors, Pennsylvania. 
Mordant for aniline-black. Prepared mixture of bichromate, etc., for application in 
dyeing with anilin black. 
Sodium sulfate and bichromate dissolved in dil. HCl to saturation at boiling temp., cooled 
to crystallize, dried and packed in jars for market. 


394 DIGEST OF PATENTS 


330,275—Nov. 10, 1885. Martin E. Watpstein and Armand Mutter, New York. 


Composition of matter to be used in dyeing. Sulfonated fatty acid compounds of 
anilin for dyeing anilin black. 


Sulfo RICINOLEIC acid, sulfo oleic acid or other sulfo comp. of fatty acid, mixed with equal 
parts ANILIN oil, as free as possible from toluidin and other homologs, and neut. by alkali, 
preferably NH,. Proportions may vary but should be nearly equal. 


331,777—Dec. 8, 1885. Alexandre N. Dusors, Pennsylvania. 
Dyeing aniline-black. 


Fabric prepared by cooking in bath of soluble castor oil, then placed in acid dye bath con- 
taining ANILIN oil, nitrate of iron and bichromate, and finished in soap bath. 


843,793—June 15, 1886. Oscar BreLtscHowsk1, New York. 


Dyeing cotton fiber. Dyeing and printing cotton and other fibers a brown color fast to 
light, air, soap and acids. 
I-NAPHTHYLAMIN in dil. HCl bath applied as usual to fiber, then soln. of bichromate and 
sulfuric acid slowly added and both gently heated. Quicker oxidization results from alum, 
Na,CO, and lead acetate preparation added to oxidizing bath. Printing process described. 


390,842—Oct. 9, 1888. Benjamin F. Cresson, Pennsylvania. 
Dyeing aniline-black. (Product also claimed.) Mixture for anilin black dyeing. 


(a) Aq. soln. of potash, NH,Cl, CuSO,, nitrate of Fe, gum tragacanth. (b) HCl, tartaric 
acid and ANILIN oil mixed with aq. ‘Two solns. mixed for use in dyeing. 


891,315—Oct. 16, 1888. Jacques Grinuut, England. 


Process of dyeing aniline-black. Dyeing cotton, jute, etc., with anilin black on azo 
dye as bottom color. 


Fibers first boiled in alk. carb. soln. with conco RED, or other azo dye, washed and worked 
in soln. of ANILIN oil, bichromate and HCl, then treated with oil, acid, dil. alkali, soap, and 
again with dye (Hessian Blue) soln. at boil. 


409,819—Aug. 27, 1880. John BracEWwELL, Massachusetts. 
Aniline-black discharge. Anilin black with clear discharge effects. 


Cloth treated with prepared ANILIN mixture is partly dried by steam, etc., above 33°, then 
drying completed below 33° to prevent too rapid oxidation and alkali discharge is then printed 
before anilin is oxidized. 


409,820—Aug. 27, 1889. John BraceweEtt, Massachusetts. 
Pigment-resist. Pigment resist pattern with anilin black ground. 


Pigment and alkali mixture printed on cloth, dried, and cloth then printed, padded, etc., 
with ANILIN mixture containing oxidizing agent and catalyst. Cloth steamed to age and develop 


color. 

409,821—Aug. 27, 1889. John BracEwELi, Massachusetts. 

Process of printing aniline-black. Printing clear discharge effects on anilin black 
ground. 


Mixture of ANILIN salt and of ANILIN oil to neutralize excess acid, with ferrocyanide paste 
is applied to fiber which is dried as shown in 409,819. Details for printing discharge, fixing, 
etc., are given. Ferrocyanide paste is made from equivalent proportion of Na,Fe(CN), and 
KCIO, boiled in starch paste. 


409,822—Aug. 27, 1880. . John BracEWwE.ui, Massachusetts. 
Aniline-Black. Printing anilin black with clear discharge effects. 

Ferrocyanide (or ferri salt) together with chlorate free from HCl is used for padding with 
prepared ANILIN, so as to retard oxidation before discharge is printed. 


409,823—Aug. 27, 1889. John BracEwELL, Massachusetts. 
Process of printing on aniline-black. Producing colored patterns on anilin black 


grounds by action of live steam. 
Cloth first printed with pattern in an alkali resist colored with pigment, is treated with 
prepared ANILIN BLACK, dried, and color and resist pigment developed by steam under pressure. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL, 395 


452,324—May 12, 1891. Heinrich Tuirs, Germany. (Cleff, 14.) 
Process of dyeing aniline-black. Dyeing and printing cotton, silk, wool and mixed 
fabrics with -anilin black. 


ANILIN mixture is composed of copper carbonate, ammonium bicarb., chlorate, HCl, and 
hydrofluoric acid to replace part of acid, proportions being varied for cotton and for wool. For 
printing, vanadium, cerium, Fe, Cr or Cu comps. are used with chlorates. History of develop- 
ment of processes given in detail and advantages of patent. 


491,673—Feb. 14, 1893. William Browninc, England. (Arnold.) 


Process of printing colors with aniline-black. Printing colors on cotton, in con- 
junction with anilin black. 


Fiber padded with tannin or other astringent, fixed by tartar, etc., is washed, dried, and 
padded with ANILIN BLACK mixture and before ageing is printed with the other color mixture 
containing sod. acetate or other resist and steamed. ‘The standard chlorate, ferrocyanide, anilin 
oil and HCl mixture is used and printing mixture contains Methylene Blue, or other together 
with methyl alc., acetate and gum. 


491,951—Feb. 14, 18093. Frank P. Pearson, Massachusetts. (Arnold.) 
Printing colors with aniline-black. Anilin black printing by chemical process. 


Fabric is padded with anilin black mixture (ANnILIN, chlorate, ferrocyanide, HCl) dried, 
printed with color resist (acetic acid, ANILIN GREEN, starch, gum, acetate, tannic acid and aq.) 
then steamed. Preferably it is also passed through bath of Sb or Sn salt. 


491,961—Feb. 14, 1803. George Donatp, Massachusetts. (Arnold.) 
Printing colors with aniline-black. Anilin black printing shortened to two operations. 


Material is padded with astringent, dried, padded with ANILIN mixture containing Sb. or 
other salt, dried, printed with color resist, aged, etc. Or material is padded with anilin mix- 
ture and astringent, dried, printed with color resist mixed with metallic salt, steamed, etc. 


499,410—June 13, 1893. Otto P. Amenp, New York. 
Process of dyeing anfline-black. 


Fiber is immersed in chromic acid HCl, wrung out, immersed in second bath of ANILIN 
or other amin and ferric sulfate or other, excess soln. removed and temp. raised to 80°. 


499,688—June 13, 1893. William T. WuiteHEAD, Canada. (Dupee, %.) 
Aniline-black discharge. Printing discharge effects on anilin black background. 


Cloth is saturated with anilin black mixture, dried enough to prevent spreading and printed 
by a discharge consisting of a zinc comp. (oxide, hydrate, or carbonate) in aq. starch paste soln. 
For colored effects a suitable dye or pigment color may be printed with the discharge. Albumen 
in the discharge paste will tend to fix the color. 


499,689—June 13, 1808. ; William T. WHITEHEAD, Canada. (Dupee, %.) 
Aniline-black resist. Zinc oxide compounds as resists for anilin black. 


Pattern is printed on cloth with resist containing zinc compound, such as oxide, hydrate, 
carbonate, etc., in aq. with a starch paste as thickener, dried and dyed or padded with an1LIN 
BLACK as usual. 


499,691—June 13, 18093. William T. WuitrenEap, Canada. (Dupee, %.) 
Aniline-black discharge. Printing white or colored discharge patterns on anilin black 
ground. 


Patent is same as 490,688 except that finely divided metallic zinc is added to zinc comps. 
wherever reference is made to these in discharge mixtures. 


499,692—June 13, 1893. William T. Wuireneap, Canada. (Dupee, %.) 
Aniline-black resist. Printing anilin black with white or colored resists. 


Patent is same as 499,689 except that finely powdered zinc is added to zinc compounds used 
in the resist paste. 
26 


396 DIGEST OF PATENTS 


500,558—July 4, 18093. John Brackwe.u, Massachusetts. 


Printing aniline-black. (Product also claimed.) Improvement in printing colored dis- 
charges on anilin black. 
A mordant is mixed with the coal tar color in the discharge. Alizarin colors with an 


aluminum salt as mordant, mixed with discharge, are printed on the black color, steamed and 
aged in such manner that the colors are simultaneously developed. 


529,498—Nov. 20, 1894. Ferdinand V. Katias, Germany. (Ochlens 


Dyeing aniline-black. Dyeing and printing with black on animal fiber by first slightly 
oxidizing the wool, etc. 


White goods treated while moist for 0.5-1 hour in bath of 6-10 per cent hypochlorite and 
9-15 per cent HCl, washed, dried and padded or printed with mixture of anit1n HCl, sodium 
chlorate, yellow prussiate and glycerin or sugar, and preferably some tartaric acid, developing 
by steam as usual. Formula for printing is given and other reagents claimed. 


529,499—Nov. 20, 1894. Ferdinand V. Katias, Germany. (Ocehler.) 
Producing figures on anilin-black. Developing and discharging anilin black simul- 
taneously. 


Fabric prepared as in 529,498, padded or printed with mixtures suitable for steam anilin 
black and for discharge white or colored figures, is steamed as usual, thus developing the black 
and discharging white simultaneously. 


539,550—May 21, 1805. Hugo Scuweitzer, New York. (Schweitzer.) 
Process of printing figured anilin-black. Printing figured anilin black by resist or 
discharge. 


Printing paste consists of 2-NAPHTHOL in alk. soln. with gum tragacanth, 4-nitro PHENYL 
nitrosamin, or other, and oxid of zinc mixed to proper consistency for printing either as resist 
or discharge. Other components claimed. 


542,046—July 2, 1805. Philip Finxeiste1n, New York. 
Dye. Mixture for dyeing with anilin black, etc. 


ANILIN BLACK, sulfuric acid, glauber’s salts and pepsin with or without soda or ammonia, 
are diluted with aq. for dye bath. 


570,117—Oct. 27, 1806. Victor G. Biorpe, Maryland. (Bloede.) 
Process of dyeing anilin-black. Anilin black dyeings by shorter and cheaper process. 

When hydrogen peroxide, chromic, perchlorous or permanganic acids act upon an anilin 
salt in presence of minimum amount of water, anilin black is produced at once. Fiber is 
soaked with soln. of anilin HCl, with or without a chlorate and a metallic salt, and without 
aging, a strong oxidizer is applied so that excess moisture is not present until oxidation is — 
accomplished. 


577,295—Feb. 16, 1807. William J. Grawitz, France. 
Process of dyeing. Dyeing anilin black without tendering the fiber. 

Instead of AnILIN HCl or homolog usually employed, the sulfo-cyanate of anilin, etc., is — 
formed by using dye mixture of anilin salt and a sulfocyanate of Ba, or NH, (which by double © 
decomp. will yield anilin sulfo cyanate) the color being developed by oxidation with chlorate © 
in presence of a salt of vanadium. : x 


588,3887—Aug. 17, 1897. Victor G. Biorpse, Maryland. © 
Process of dyeing. Improved process for dyeing anilin black or homologs. ' 


metallic salts of Fe or Cu, then treated with 1-10 per cent chlorine gas or other gaseous or ~ 


‘ 

Fiber is impregnated with ANILIN salt, chloride, acetate, or tartrate, etc., with or within 
vaporized oxidizing substance. “ 
» 

A) 


588,38S—Aug. 17, 1897. Victor G. Biogpr, Maryland. 
. Process of dyeing anilin-black. Improved process for dyeing anilin black, etc. 
Fiber is impregnated with ANILIN salt or its homologs, preferably slightly basic, mixed with | 
neutral or slightly acid chromate, chlorate, nitrate, or other, in equivalent proportion for oxida- 
tion of anilin, and subjected to fumes or vapor of a volatilized acid, capable of displacing alla 
or part of the oxidizing element. HCl is preferred as the acid. | 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 397 


592,022—Oct. 19, 1807. Re. 11,647—Dec. 29, 1897. 
Henri N. F. Scuarrrer, New Hampshire. 


Process of dyeing mixed goods. Dyeing mixed cotton and wool goods a fast black. 


Wool portion of goods is first dyed by ALIZARIN BLACK, then cotton fiber dyed with ANILIN 
BLACK. Full details of both processes given. 


727,292—May 5, 10903. Friedrich Crerr, Germany. 
Process of dyeing and printing in anilin-black. Improvements in dyeing with 
anilin-black, free from greenish cast and from injury to fiber. 

Dye mixture consists of KCIO,, NH,Cl, Cu(NO,),, anrz1n and Formic acid instead of min- 
eral acids formerly employed. Printing comp. also contains formic acid. For wool a prelim- 
inary treatment with Ca(OCl), or KMn0O, is required. 

Note 452,324. } 


779,228—Jan. 3, 1905. Heinrich Mann, Germany. 
Process of dyeing. Dyeing with anilin black and related colors by simpler, cheaper, and 
more exact method. 

ANILIN or other amins or oxy. deriv. of benzene or naphthalene or a tertiary amin, is 
mixed with FeCl, or other colored metal salt and H,O, equivalent to half mol. anilin, etc., and 
dyed on fiber in bath at 80° with or without organic acid present, and in absence of mineral 
acid or alkali. 


830,082—Sept. 4, 1906. Franz Konitzer, Germany. 
Process of dyeing wool black. Dyeing mixed fiber with oxidation black. 
Wool fiber alone or mixed fabric is first dyed blue in bath of potassium ferricyanide or 


other cyanide and sufficient acid, then two fibers together are padded with aniniIn and oxidiz- 
ing agent, dried, aged, chromed, steamed, etc., as usual. 


959,516—May aT TOL. Arthur G. Green, England. 
Production of anilin black on fibers and fabrics. Process for aging anilin black 


without weakening fiber. 

ANILIN is oxidized on fiber by air using a small amount of a catalyst such as 4-PHENYLENE 
DIAMIN, or other comp. capable of forming an indamin, together with a copper or vanadium 
salt. As no free acid is liberated in process the fiber is not tendered. 


963,656—July 5, toro. Henri Scumip, Germany. (Badische.) 
Producing brown, olive, and green shades on the fiber. 


Amino PHENOL, or other, is oxidized by chlorate and ferrocyanide on fiber, steamed, 
chromed, and washed in acid or alkaline bath to shade desired. Discharge process also given. 


1,019,576—Mar. 5, 1912. 
; Richard WoLFFENSTEIN and James CoremAn, Germany. (Berlin.) 
Hair-dye. MHair dye that will not irritate skin. 
4-TOLUYLENE DIAMIN, or other aromatic diamin, is mixed with equal parts anhyd. normal 
sodium sulfite, in 3 per cent H,O, soln. for application to hair to produce according to con- 
centration varying shades of blond to brown or black colors. 


1,144,18i—June 22, tors. 
Arnold Ernuenspacnw and Karl Marx, Germany. (Berlin.) 


Dyes for furs, hairs, and the like. Stable commercial form of fur dyes, ready for use. 
4-Amino dimethyl anin1n sulfate, 4 parts, is mixed with 3 parts amino ANIsiIpIN sulfate 
(2.4-diamino anisol). For dyebath the calculated quantity of a base such as NH,OH must be 
added to neut. liberated acid. Fur preferably is mordanted with FeSO,. 
Note 1,105,501, 1,105,554 and 1,144,325 for related patents. 


1,144,325—June 22, 1915. Arnold Ernensacu, Germany. 
Preparation for dyeing hairs, furs, and the like. 
4-TOLUYLENE DIAMIN sulfate, the methoxy deriv. or other, 2 parts, is mixed thoroughly with 
I part 4-amino ANISIDIN (2.4-diamino anisol). For dye bath ammonia is added to neut. lib- 
erated acid and H,O, to oxidize. Furs are mordanted with FeSQ,. 
Addition to 1,105,554 and 1,144,181. 


398 DIGEST OF PATENTS 


1,183,748—May 16, 1916. Karl Marx, Germany. (Berlin.) 


Process for dyeing skins, hairs, and the like. Dyeing skins, hairs, etc., without 
adding an alkaline substance. 
Skin to be dyed is well washed in dil, Na,CO,, rinsed and dyed with dimethyl 4.4’-diamino 
DIPHENYLAMIN or deriv. and H,O,. Gray developed dye. 


1,277,056—Aug. 27, 19018. Re. 14,824—Mar. 23, 1920. Emile A. Fournraux, England, 


Production of black upon textile fibers. (Product also claimed.) Anilin black on 
fibers. 

ANILIN or mixtures of primary amins, but not amino DIPHENYLAMIN comps., with not ex- 
ceeding 3 out of 11 parts of amins substituted in para position to NH,, a strong mineral acid 
(HCl or HNO,) in such proportion as not to interfere with formation of nigranilins, formic 
acid to prevent undesirable brown by-products, thickener, boric acid to prevent loss of anilin 
(or phosphoric or meta phosphoric acids) chlorates of alk. metals as oxidizers, an organic cata- 
lyst, preferably 4-phenylene diamin, an inorganic catalyst, preferably a sol. Cu salt (for print- 
ing, insol. salt such as CuS) and for padding purposes lactic acid, are present in dye soln. 
Various conditions are discussed. 


1,350,600—Aug. 24, 1020. Emile A. Fournraux, England. 
Production of anilin black upon vegetable textile fibers. (Product also 
claimed. ) 


Dyebath contains ANILIN, a strong mineral acid, formic, metaphosphoric, and boric acids, 
thickener, chlorates of alk. metals, an organic catalyst such as 4-PHENYLENE DIAMIN, an inorganic 
catalyst (Cu, V) and color is developed on fiber by drying in hot air and chroming. 

Note 1,277,056. 


1,417,206—May 23, 1922. Albert W. Scumin, Switzerland. 
Process for weighting or charging silk to be dyed black. 


Silk is weighted by usual tin phosphate process then treated in boiling lather or froth bath 
of haematein, an alk. substance such as sod. silicate and chrysalides. 


SUBGROUP III.—-ANTHRAQUINONE. (An.) 


4,192—Sept. 13, 1845. Frederick Pranner, Rhode Island. 
Improvement in preparation of dye-stuff from spent madder. Reclaimed 
spent madder. 
Spent madder is extracted by 1° sulfuric, drained, and again treated with dil. soda, filtered, 
dried and pulverized. Rep vat dye. Called by trade mame ‘‘Carasene.” 


74,935—Feb. 25, 1868. Alfred Parar, Massachusetts. 
Improved process of separating coloring matter from madder and other 
plants. Purified madder. 

Madder root is dried, pulverized, sugary matters extracted by water, and drained root 
digested several days with ammonia water and copper turnings to dissolve ligneous matters 
(38 per cent) adjusting amounts so that all is dissolved with neither excess Cu or NH,. The 
copper compound of the color thus formed is filt. off, mixed with alc., and H,S passed in to 
ppt. CuS. Modified methods are given. 


86,939—Feb. 16, 1869. Alfred Parar, New York. (Gerson.) 


Improved process of extracting the coloring-matter of madder. Purified 
madder color, ‘Tinctorine.” 

Dried, ground madder root, is freed from sugary matter by extraction with aq. at moderate 
temp., (soln. may be used to produce alcohol) then boiled in dil. H,SO, (25°) for 2 hours to ~ 
remove resinous matter, drained, washed free of acid and this so-called “‘Garancine” digested 
with steam under 50-60 lbs. pressure (302-305° F.) to extract coloring matter, which is sol. at 
high temp., and is deposited from soln. upon cooling. 

Called ‘‘Tinctorine.”? For product patent, see 93,900. 


93,900—Aug. 17, 1860. Alfred Parar, New York. 
Improved. material for dyeing and printing, obtained from madder. Puri- 
fied madder color, or ‘“Tinctorine.’’ M 


By process shown in 86,939, pectic acid and pectins, which render printed madder soluble — 
when steamed, are removed by discarding the first portion of the steam extract. Copper com- $ 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL, 399 


pounds, which dull the shade are not present. Pure alizarin and purpurin as extracted by ex- 
pensive processes are not suited for printing by reason of absence of all fatty matters, which 
by process claimed are present in ‘‘Tinctorine.” 


95,039—Sept. 21, 1869. Alfred Parar, New York. (Renwick.) 


Improved extract of madder for dyeing and printing. Compound of madder 
with alkaline base and volatile acid. 


When steamed upon cloth a mixture of madder with an alkali salt of a volatile acid will 
decompose, the acid will be removed, and base will develop or brighten the color of the madder. 
Patent gives formulas and methods of mixing for compounds containing preferably ‘Tinctorine’”’ 
with acetic acid, rancid olive oil, acetate of lime (R), of alumina (R) or of iron (V) and 
starch, (to give consistency to compound); RED to VIOLET (purple) vat dyes. 


110,994—Jan. 17, 1871. Alfred Parar, New York, (Renwick.) 


Improvement in material called ‘“Ole-izerine,’”? for dyeing and printing. 
Purified madder or ‘‘Ole-izerine.”’ 


Madder, after treatment to remove sugars and resinous matters, (then called “Garancine’’) 
is extracted with petroleum oil of suitable boiling pt. (150-175°) which removes color that is 
recovered from petroleum solvent by dil. aq. alk. and pptd. from the latter by acid. Product 
is specially fitted for printing and for making ‘‘Rubidide.”’ 

Note 113,918. 


113,91 8—Apr. 18, 1871. Alfred Parar, New York, (Renwick.) 
Improvement in products made from madder. -Additional product from madder, 
or “‘Oil-izarine.”’ 

Process is same as that used in 110,994. Purified madder or ‘‘Garancine’’ is extracted three 
times with kerosene or other hydrocarbon and liquid removed for recovery of dissolved color. 
The present patent preserves the exhausted matter or dregs, which are placed in bags, pressed, 
and used as madder dye under the name of ‘‘Oil-izarine.”” (Note changed spelling.) 


113,9198—Apr. 18, 1871. Alfred Parar, New York. (Renwick.) 


Improvement in compositions of madder for printing cloths, ete. Madder 
compound—‘“‘Rubidide.”’ 


Purified madder such as alcohol extract of madder root or “Garancine,” ‘‘Tinctorine,”’ etc., 
is boiled either moist or dry with equal weight pure glycerin. Apparently a chemical combina- 
tion takes place and ‘‘Rubidide,’”? which is believed to be the alizaric and purpuric ethers of 
glycerin, is formed. 


182,234—Sept. 12, 1876. Richard Simpson, Arthur Brooke and Thomas Royse, England. 
Improvement in preparation of alizarine, etc., made from anthracene. Dry 
lime salt of alizarin in marketable form. 


ALIZARIN is prepared as lime salt, dry powder, by mixing coloring matter with dil. hydrate 
of lime, filtering, drying and pressing through sieve. 


243,378—June 28, 1881. Armand M. Jacoss, Russia. (Burtnett.) 


Turkey-red mordant. Sodium salt of sulfonated vegetable oil mixed with ammonia, for 
Turkey Red mordant. 


Vegetable oils such as castor, olive, sunflower seed or rape seed oils, are cooled in a wooden 
tank while about 0.2 parts H,SO, (1.81-1.85) are added slowly, keeping temp. below 55°, let 
stand 12 hours, neut. with aq. Na,CO,, let stand 24 hours, separated and mixed with about 0.1 
part aqua ammonia. 


245,6323—Aug. 16, 1881. Armand M. Jacoss, Russia. (Burtnett.) 


Process of manufacturing oleaginous mordants. Sodium salt of oxyoleic or rici- 
noleic acid for Turkey Red mordant. 


Any vegetable or animal oil, fat, or oleic acid, mixed at 8° with 25-30 per cent H,SO, 
(1.82-1.83) stirring constantly, until temp. reaches 39-40°, then 2 parts cold aq. added, reducing 
temp. below 10°, let stand 2 days, separated and boiled in aq. to separate fatty acids and sul- 
furic, the former separated and neutralized with alkali. 


400 DIGEST OF PATENTS 


258,531—May 23, 1882. Heinrich Bruncx, Germany. (Badische.) 


The production of blue colors upon textile fabrics. (Product claimed.) Dyeing 
-fiber with alizarin blue. 


ALIZARIN treated as in patent 258,530 to produce ‘“‘Anthracene Blue,” is added to fiber, 
(which may previously have been treated with acetic or tartaric acids, or Ca, Mg or Cr salts 
of these acids) and heated to 70—-100° or steamed to develop color. 

S. 804—‘“‘Alizarin Blue S.’ 


261,600—July 25, 1882. Johannes H. H. O. Gttrxzt, Germany. (Héchst.) 


Production of soluble alizarine-blue color. Soluble ammonium sulfite compound 
of alizarin blue. 


ALIZARIN BLUE, 10 per cent paste, or its alk. salt, mixed with neutral (NH,),SO, and heated 
to 30-40°, soln. filt. and pptd. by NaCl. 
S. 804—‘“‘Alizarin Blue S.” 


263,964—Sept. 5, 1882. Heinrich Rost, Germany. (Héchst.) 


Manufacture of dye-stuff from alizarine-blue. (Product, not process, claimed.) 
Alizarin blue printing compound. 


ALIZARIN BLUE, Na salt as paste, is mixed with thickener, with NaHSO, or other alk. sulfite, 
and with acetate of chrome or other mordant. 
Note 261,600 and 263,965. 


263,965—Sept. 5, 1882. Heinrich Rose, Germany. (Héchst.) 


Manufacture of alizarine-blue color. (Product also claimed.) Alkaline bisulfite 
compound of alizarine blue. 


Alkali salt of Alizarin Blue (ALIZARIN quinolin) is first formed by adding alkali or alkali 
carb. to aq. suspension of dye, then alkaline bisulfite added as conc. soln. in excess whereby 
the alizarin blue dissolves quickly and its bisulfite comp. crystallizes out in part, and is com- 
pletely pptd. by salt. 

Note 263,964. 


274,081—Mar. 13, 1883. Heinrich Brunck, Germany. (Badische.) 
Manufacture of anthracene-blue. _1.2-Dioxy anthraquinolin bisulfite salt. 


Alizarine blue (ALIZARIN quinolin) obtained as in 258,530, dry crystals, is mixed with 2 or 
more parts bisulfite soln. (Sp. Gr. 1.25) and an assistant, such as 10-15 per cent alcohol, or 
acetic acid or ester. Bisulfites of Ca, Mg, Zn, Mn, Al, Cr, or Fe may be used instead of alkali 
salts. 

S. 804—‘“‘Alizarin Blue S.” 


379,150—Mar. 6, 1888. René Boun, Germany. (Badische.) 
Dyeing animal textile fabrics with naphthazarin. (Product also claimed.) 

Animal fibers dyed with naphthazarin on chrome mordant, and process therefor. 

Wool boiled in soln. of bichromate and bitartrate, is washed and dyed in 1o per cent paste 
of NAPHTHAZARIN, raising temp. from 30° to the boiling point. To correct alkalinity of water 
in dye bath, a little acetic acid is added (1:1000). Other chrome mordants and other acids are 
claimed. Dye gives slate GRAY to BLACK colors, fast to light, air, soap and acids. 

S. 774—‘“‘Alizarin Black.” 


481,591—Aug. 30, 1892. Henry N. F. Scuarrrer, Massachusetts. 
Process of dyeing with alizarin. Soluble compounds of alizarin or boro-alizarates of 
alkali, easily decomposed by mordant in dyeing process. 
Commercial ALIZARIN paste, dried, is mixed with 2 parts borax, or other soluble borate, 
boiling aq. added and soln. used as dye bath or dried to powder for marketing. Fiber is im- 


pregnated with borate compound then passed through mordanting bath. Similar comps. or 
homologs and derivs. of alizarin are claimed. 


527,457—Oct. 16, 1894. Henri N. F. Scuarrrer, Massachusetts. 


Soluble alizarin blue. (Process also claimed.) Soluble form of alizarin derivs. un- 
affected by boiling temps. ; 


Alizarin dye is rendered anhydrous, mixed with 2 parts dry boric acid, heated to fusion, 
cooled, ground, warmed and mixed with alkali to thick paste. Product is aq. sol., not decomp. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 401 


-on boiling, dyes wool with usual mordants without pptn. in bath, and dyeings will not rub off. 
Note 258,530. 


612,274—Oct. 11, 1808. John T. Reip and Henry Tuorp, England. 
Dyeing textile fibers, yarns, and fabrics. Dyeing and fixing Alizarin Blue S with 
Cr and Fe salts to produce khaki shades. 
Fiber is treated with olein oil and aq., dried and impregnated with dye liquor consisting 
of mixture of acetates of Cr and Fe, Alizarin Blue S and a bisulfite, mangled, dried and 
exposed to steam at 4 lbs. pressure, then color fixed by alk. bath, etc. 


631,906—Aug. 29, 1899. John T. Remp and Henry Txorp, England. 
Process of dyeing Khaki. Dyeing khaki shades with Alizarin Blue S on Cr and Fe 
mordants. 


Process outlined in 612,274 is simplified by omitting olein oil.treatment. Otherwise process 
is the same. Other anthracene dyes such as Gallein, Cerulein, etc., are claimed. 


633,438—Sept. 19, 1899. Franz Erspan, Germany, and Leopold Srrcut, Austria-Hungary. 
Process of dyeing. Dyeing loose textile material with alizarin dyes. 


Goods are impregnated with any alizarin dye (long list given) in alk. soln. (ammonia, its 
salts, alk. hydroxide or carbonate, or any alk. salt or soap, especially those that are volatile), 
dried, and fixed in a mordant bath of Al, Cr, Ca, Fe, etc., as salts of volatile acids, and finally 
steamed. 


649,486—May 15, 1900. Robert E. Scumipt, Germany. (Elberfeld.) 


Process of dyeing. Dyeing with amino oxy anthraquinone sulfo acids with reducing 
agents present to prevent reddening of shade. 


One hundred parts of woolen fabric are dyed in 1500 parts aq., containing 2 parts dye 
(diamino anthrachrysone disulfo acid, diamino anthrarufin or diamino chrysazin sulfo acids, or 
other amino oxy anthraquinone sulfo acid) 1 part sodium bisulfite and 3 parts 66° sulfuric acid, 
in usual manner at 100°. Sulfurous acid or other bisulfites may be used as reducing agents. 


661,858—Nov. 13, 1900. Alvin FAEHRMANN, Germany. (Badische.) 


Process of dyeing Turkey Red. Simplified process of dyeing Turkey Red. 

Boiled and washed cotton fiber in 2-lb. lots-is passed through a special oiling bath (stock 
soln.—14 parts NaOH, 25 parts Na,SnO,, 15 parts Na,Al,O,, and 1o parts HNa,PO, in 200 parts 
boiling aq., 100 parts castor oil added, mixture boiled until saponified, then dild. to 850 parts, 
(to give density of 10°.) wrung out, dried at 60—70° and mordanted in Al,(SO,), bath containing 
NH,Cl and MgSO, at 35-40°, which bath must be acid in reaction, washed free of acid and 
without drying dyed in 1.5-2 per cent alizarin bath containing acetate of lime. 


746,784—Dec. 15, 1903. Rene Boun, Germany. (Badische.) 
Process of dyeing textile fiber blue. (Product also claimed.) Dyeing blue with 
Indanthrene. 


One part of Indanthrene is suspended in 500-1,000 parts aq. at 50-60°, to which 20-30 
parts sod. hydrosulfite (10 per cent) and 10-15 parts NaOH (24 per cent) are added. Forms blue 
soln. that can be applied to the fiber as with indigo vat. Dyed fiber is changed to green or 
yellow with Cl, HNO, or CrO, and restored to blue by hydrosulfite. 


772,237—Oct. 11, 1904. Paul JEANMAIRE and Rene Boun, Germany. (Badische.) 


Printing with indanthrene. (Product claimed.) Improved process for printing ind- 
anthrene. 

Fiber is printed with paste containing indanthrene, tin salt and thickening agent, dried and 
treated 0.5 minute at 65-75° with 13-14.5 per cent soln. of NaOH. Modified processes also 
described and other components. Dyed fiber with HNO,, CrO, or acid KMnO, turns (G-Y), 
restored to (B) by hydrosulfite. 

Note 682,523 Gr. III. 


840,419—Jan. 1, 1907. Oscar Batiy, Germany. (Badische.) 


Process for dyeing textile fiber violet-blue. (Product also claimed.) Developing 
benzanthrone indanthrene on the fiber or as print color. 
BENZANTHRONE, produced by condensing 2-amino ANTHRAQUINONE with GLYCERIN, dissolved 
at 90-95° in very dil. alk. hydrosulfite, and fiber worked in this vat, washed, dried, acidified, 


402 DIGEST OF PATENTS 


and again washed. For printing the paste contains SnCl, and FeSO, and after drying is passed 

through a bath of dil. NaOH at 65-75°, (using MnO, to clear the whites), washed and iron 

removed by acid. Dye is violet BLUE, fast to HCl, redder with NaOH and with conc. sulf. (V). 
Note 809,892, 818,992, and 820,379 Gr. III. 


893,384—July 14, 1908. Arthur ScHLEGEL, Germany. (Badische.) 
Dyeing. Dyeing with indanthrenes or other vat colors of the anthracene series. 
Dye is mixed with thickener to very fine paste, strained and applied to the goods in print- 


ing or padding machine, fabric dried or not, and heated at 60-65° in dil. alk. hydrosulfite, 
washed, acidified, washed again, etc. 


938,616—Nov. 2, 1909. Paul THomascHEwski, Germany. (Bayer.) 
Anthracene compound. Leuco form of dibenzoyl 1.8-diamino anthraquinone. 

Dibenzoyl 1.8-diamino ANTHRAQUINONE reduced to leuco form by heating in alk. hydrosulfite. 
Sod. salt is a brown cryst. powd., with air (Y), sol. in aq. (RBr), in conc. sulf. (G-OY), when 
oxidized forms orig. comp.; an orange YELLow vat dye. 

S. 817—“‘Algol Yellow.” Note 938,617 and 938,619. 


938,617—Nov. 2, 1909. Paul THomascHEewski, Germany. (Bayer.) 
Anthracene compound. Letuco form of dibenzoyl 1.5-diamino anthraquinone. 

Dibenzoyl 1.5-diamino ANTHRAQUINONE is reduced to leuco form by heating in alk. hydro- 
sulfite. Sod. salt is pale cryst. powd., with air (Br-Y), sol. in aq. (VBr), in conc. sulf. (G-OR), 
forms orig. comp. when oxidized; an orange YELLOW vat dye. 

S. 817—“‘Algol Yellow.R.”’ Note 938,616, 18 and 19. 


965,804—July 26, 1910. Emil Franke, Germany. (Ordnau.) 
Alizarin preparation and process of making. Dry, soluble and conc. alizarin or 

derivs., for dyeing and printing. 

ALIZARIN heated with sufficient alk. to form mono alkali salt, is boiled to dryness with 
sodium salts of organic or boric acids, Products are easily soluble. 

S. 778—‘‘Alizarin.” 


968,376—Aug. 23, I9I0. Arthur LurtrincHaus, Germany. (Badische.) 
Pigment. Yellow anthraquinone dye lake. 

NAPHTHANTHRAQUINONE (from phthalic anhyd. and naphthalene comp.), homologs or derivs., 
is pptd. with aluminum hydroxide or sulfate, BaSO,, etc., as substrata to form yellow lakes 
which are fast to aq., lime, light and oil. ; 

S. 758—‘‘Sirius Yellow G.” Note that patentee has applied a previously known compound 
to lake formation. 


970,07 2—Sept. 13, 1910. Ernst Mrecxspacu, Germany. (Bayer.) 
Yellow lake. Dibenzoyl 1.8-diamino anthraquinone lake. 

Dibenzoyl 1.8-diamino ANTHRAQUINONE (a) is pptd. with BaSO, or aluminum salts, (b) or 
reduced in hydrosulfite vat, Al,(SO,), added and lake pptd. by blowing air and CO, into the 
mixture, (c) or ground with heavy spar and a little aq. Yrtiow lake, fast to light, aq., and 
oil. 

Note 970,073 and 938,616, et seq. 


970,073—Sept. 13, 1910. Ernst Mrcxsacu, Germany. (Bayer.) 
New Yellow lake. Dibenzoyl 1.5-diamino anthraquinone. 

Dibenzoyl 1.5-diamino ANTHRAQUINONE is pptd. by Ba or Al salt, as in 970,072. YELLOW 
lake, fast to aq., light, oil. 


970,340—Sept. 13, 1910. Filip Kacer, Germany. (Badische.) 
Anthracene compound and process of making same. Leuco form of 2.2/-di- 
methyl 1.1’-dianthraquinonyl amin. 
2.2’-Dimethyl 1.1/-DIANTHRAQUINONE amin, is reduced in alk. soln. with hydrosulfite. Pro- 
cess for printing or dyeing on fiber given. Product is sol. in alk., and when applied to fiber 
and oxidized, gives tints of RED (pink) dyeings, fast to alk., acid, Cl. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 403 


972,066—Oct. 4, 1910. Joseph Drinet, Germany. (Bayer.) 
Process of dyeing and product thereof. Dibenzoyl 1.5-diamino anthraquinone. 


Dibenzoyl 1.5-diamino ANTHRAQUINONE, 100 parts of 10 per cent paste, 74 parts tragacanth 
etc..—methods for dyeing cotton and wool described. Dyeings are not changed by boiling 10 
per cent HCl, by cold conc. H,SO,, or dil, KOH; yvetLow vat (Y-GBr) dye, fast to acids 
and alks. 

S. 817—“‘Algol Yellow R paste.”” Note relation of this patent to 938,616. 


978,138—Dec. 13, 1910. Joseph Deringer, Germany. (Bayer.) 
Printing-paste. lLeuco dibenzoyl 1.5-diamino anthraquinone. 


Dibenzoyl 1.5-diamino ANTHRAQUINONE, 10 per cent paste, is reduced in hydrosulfite vat, 
(65:1000), 1.1 parts tin crystals, 7 parts copperas, and 8 parts tartaric acid are mixed for 
printing paste, printed on fabric, run through NaOH (18°) at 85°, made acid, rinsed and soaped 
at 60°. 

S. 817—“‘Algol Yellow R., paste.”’ Note 938,616,-17 and -18 and 978,139. 


978,139—Dec. 13, 1910. Joseph Deinet, Germany. (Bayer.) 
Printing-paste. lLeuco compound of dibenzoyl 1.8-diamino anthraquinone. 


Dibenzoyl 1.8-diamino ANTHRAQUINONE paste in aq., mixed with tragacanth, tin crystals, 
copperas and tartaric acid, is printed on fabric, run through soda lye (18°) at 85°, acidulated, 
rinsed and soaped at 60°. 

Addition to 978,138. 


984,545—Feb. 21, 1911. Frederick Davis, England. (Bayer.) 


Process of calico-printing. Printing with vat dyes for variegated color effects. 

Fabric is printed with a resist paste containing sulfur and a suitable alkali to which may 
be added a sulfur color, vat dye, or mixture, then is covered with suitable vat dyes such as 
indigo, indanthrene, algol, ciba, or thio naphthene colors. Resist dyes must be capable of fixa- 
tion by simultaneous action of sulfur and alkali, while practically all vat colors are available 
as cover dyes. 


1,055,701—Mar. 11, 1913. Rene Bonn, Germany. (Badische.) 


Pigment and process of making the same. [euco indanthrene, its derivs. or other 
vat color, in new physical condition readily reduced in vat, called ‘‘pigments” in patent. 
INDANTHRENE Blue RS is boiled in dil. NaOH soln., with grape sugar. Air is passed through 

soln., if dye dissolves, so that filtrate may be colorless, and amount of solvent present must be 

insufficient to dissolve coloring matter. 


1,090,852—Mar. 17, 1914. 
Carl Tuun, Paul Tust and Paul THomascHEwski, Germany. (Synthetic.) 
Red alumina color-lake. Aluminum lakes of purpurin sulfo acids. 
1.2.4-Trioxy ANTHRAQUINONE 3-sulfo (pURPURIN sulfo acid) 1.25 parts, and ro parts alumi- 
num sulfate or hydrate, are dissolved in hot aq. and 30 parts Na,CO, in soln. added. Products 
form violet RED lakes, fast to light. 
Note 1,090,353. 


1,090,353—Mar. 17, 1914. 
C. Tuun, P. Tust and P. TuHomascuewsk1, Germany. (Synthetic.) 
Red alumina color-lakes obtained from amino xanthopurpurin-sulfonic 
acids. 
t-Amino 2.4-dioxy ANTHRAQUINONE 3-sulfo, or analog, is pptd. with aluminum sulfate or 
hydrate in hot aq. sod. carbonate soln. Products form! violet rEp lakes, fast to light. 
Addition to 1,090,352. 


1,199,273—Sept. 26, 1916. Michael Inyinsky, Germany. (Wedekind.) 
Process for dyeing with dyestuffs insoluble in water or water-insoluble 
leuco compounds of dyestuffs. Vat and mordant dyeings in two stages. 

Vat dyestuffs, their leuco metal salts, mordant dyes of alizarin series, or combinations of 
these in neut., acid or alk. aq. suspension, are dyed on mordanted or unmordanted fiber as loose 
or unstable comps., then converted to stable compounds by vatting on fiber. Numerous methods 
given in detail. Uniform and well penetrated dyeings with no loss of dye result and process 
is cheapened in several ways. 


404 | DIGEST OF PATENTS 


1,126,387—Jan. 26, 1915. Johann Carstens, Germany. (Bayer.) 


Printing-pastes and process of producing same. (Printing pastes from anthra- 
quinone dyes. 


ANTHRAQUINONE dye (Algol Blue RG, etc.,) is dissolved in alkali, excess of which is 
neutralized with binding agent of weak acid character, and thickening and reducing agents added. 
Several formulae given. 


1,126,591—Jan. 26, 1915. Paul Tust, Germany. (Synthetic.) 
Alumina color-lakes. [Lakes from anthraquinone dyes. 


1.4-Dioxy ANTHRAQUINONE 2-sulfo acid, the (1.4.5) comp. or other, is pptd. as an aluminum 
lake, with or without a barium salt. Violet rED lakes, fast to light. 


1,126,664—Jan. 26, 10915. P. THOMASCHEWSKI and P. Tust, Germany. (Synthetic.) 
Color-lakes. Lakes from 1-amino 4-oxy anthraquinone sulfo acids. 


1-Amino 4-Oxy ANTHRAQUINONE 3-sulfo acid, or other similar deriv., is pptd. as aluminum 
lake with or without baryta. Vuouet lake, fast to light. 


1,145,934—July 13, 1915. A, STEINDORFF and R. WELDE, Germany. (Hochst.) 


Finely-divided wat dyestuffs and process of making same. Precipitating finely 
divided indanthrenes and removing impurities. 
INDANTHRENE colors treated at low temp. with sulfuric acid insufficient to dissolve them 
whereby the dye sulfate is formed, then water added to magma to ppt. dye in finely divided 
condition of great covering power. Impurities are removed in filtrate of diluted acid. 


1,150,863—Aug. 24, 1915. Richard Just and Fritz EckuHarp, Germany. (Badische.) 


Pigment and making the same. Pigments from indanthrene colors. 

INDANTHRENE BLUE RS (N-dihydro ANTHRAQUINONE azin) or other indanthrene color, in 20 
per cent paste is mixed with hydrosulfite and alkali, stirred slowly till oxidized, then diluted and 
filt. Color is obtained in finely divided or micro-cryst. condition, suitable for pigment. 

Note 1,055,701. 


1,175,997—Mar. 21, 1916. Albrecht ScumMipt, Germany. (Héchst.) 


Preparations from quinone wat dyestuffs. Leuco quinone vat dye in condition to 
use directly in vat. 

Alkali metal salts of leuco comps. of quinone vat dyes, such as those derived from BENZO- 
QUINONE, and 2 mols. 4-CHLORANILIN, mixed with aq. soln. of alk. salt of sulfonated ricinoleic 
acid, such as ‘‘Turcone oil,’? ‘‘“Monopole soap,” etc., are heated in closed vessel at 60° with a 
little NaOH and hydrosulfites to a limpid soln. that may be diluted and used as such or conc. 

Note 1,128,368. 


1,203,642—Nov. 7, 1916. Ernst Mrcxpacu, Germany. (Synthetic.) 
Color-lakes fast to light. lLakes from basic dyes together with polyoxyanthraquinone 
dyes. - 


ALIZARIN SAPPHIROL (diamino ANTHRARUFIN disulfo acid) or other polyoxy-anthraquinone 
dye, together with a basic dye such as Rhodulin Yellow 6G (alkylized dehydrothiotoluidin) are 
pptd. as aluminum lake, with or without baryta. GreEn lakes, fast to light. 


1,228,089—May 29, 1917. W. Beckers and I, Dreyrus, New York. (Beckers.) 


Soluble color compounds. (Process also claimed.) Soluble comp. of mordant dyes for 
direct dyeing and printing. a 
ALIZARIN BLUE or other mordant color is added to solution of glucose and neut. chromate 
which had previously been heated till all chromic acid was reduced, then neut. by acetic acid. 
A soluble chromium dye comp. results, and bath may be used as such or evaporated to dryness, 
preferably after making slightly alkaline. 


SUBGROUP V.—AZIN, Including INDULIN. (AI.) 


328,465—Oct. 20, 1885. Max Conrap, Germany. (Héchst.) 
Process of printing textile fabrics. Printing textiles with basic dyes. 

Coloring matters are fixed on fibers by printing with mixtures of LAEVULINIC acid (instead 
of tartaric acid or tartrates), oil emulsion, acetic acid, starch and tannic acid in tragacanth 
water, then steaming as usual. 


a Es 


Cy PT ih Sane elias te EE pe 


pairs 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 405 


352,361—Nov. 9, 1886. Oscar ScHRAUBE, Germany. (Badische.) 
Production of acetine-blue colors. (Product, not process, claimed.) Improved method 
of application of indulin to fiber. 


INDULIN mixed with 4 paris ACETIN is heated to 80-90° for one hour. Prepared in this 
form indulin may be used for printing without injuring vegetable fiber. 
S. 697—‘‘Acetin Blue R.” 


(354,714—Dec. 21, 1886. Clemens LouMann, Germany. 
Process of dyeing wool azodiphenyl blue. Azodiphenyl Blue or Nigrosin dye bath. 


For 100 lbs. wool dye bath contains 10 lbs. “dye mixture,” 10 lbs. NaHSO,, and 6 lbs. oxalic 
acid dissolved in sufficient hot aq. The ‘‘dye mixture” consists of 34 Ibs. Azodiphenyl Blue, 30 
Ibs. logwood extract (dry), 16 lbs. cryst. CuSO, and 20 Ibs. cryst. FeSO,. 


396,692—Jan. 22, 1880. Gottfried Grin, Germany. (Bayer.) 
Printing of induline dyestuffs. Indulin dye compounds with organic acid ethers 
which yield no free strong acid injurious in printing process. 

INDULIN paste, 45 per cent, is ground in mill at 40° with 0.25 part FoRMyYL ether till indulin 
is dissolved. Operation takes several hours. Product is adapted for printing. Formyl ether 
of glycerin may also be used in printing paste. 

Note 352,361 for acetin comp. 


418,916—Jan. 7, 1890. Benno Homoyxka, Germany. (Hochst.) 
Blue dye. Acetates of indulin base. 

Mixture of indulins as salts is treated with NaOH for 12-24 hours, bases separated, washed, 
and boiled in dil. acetic acid or other organic acid. Products are easily sol. in aq., and are 
adapted for dyeing and printing. 

Note that patent claims a new dye when in fact it is a previously patented dye in specially 
prepared form for application in printing, etc. 


475,616—May 24, 1892. Robert SENGER, New York. 


Induline dye. (Process also claimed.) Compounds of basic dyes, such as Indulin, with 
fatty acids. 


INDULIN base is combined with 3 mols. oleic acid or other fatty acid by heating together at 
I00-120°. 


SUBGROUP VI.—AZO. (Az.) 


241,661—May 17, 1881. T. and R. Horuimay, England. 
Dyeing colors on cotton or textile fabrics. (Product claimed.) Anilin azo 1-naph- 
thol, or other, developed on fiber. 

Fiber impregnated with alk. soln. of 2-NAPHTHOL, or other aromatic phenol or amino phenols, 
is submitted to action of diazo ANILIN, or other aromatic amin, then alkali applied, preferably 
NH,. Order of procedure may be reversed or otherwise changed, and mixtures used. YELLOW 
to ORANGE to rED developed dyes. 


241,661—May 17, 1881. Thomas and Robert Ho.izipay, England. 
Dyeing colors on cotton or textile fabrics. (Product also claimed.) Dyeing azo 
dyes by coupling on fiber. 
Fiber is impregnated with 2-NAPHTHOL, or other phenolic coupling agent, then treated with 
a soln. of diazo ANILIN or diazo deriv. of any suitable amin or amino phenol, etc. Mixed 
coupling or diazo reagents may he used. 


252,317—Jan. 17, 1882. Thomas Ho.iiipay, England. 
Producing azo colors upon vegetable fiber. Developing azo dyes on cotton. 


Cotton yarn prepared with oxidized sulfonated oil is steeped in 1 per cent soln. of NAPHTHOL 
or phenol, then passed through 1 per cent diazo amino azo BENZENE, or other, followed by alk. 
carb. soln. Order of procedure may be reversed. 


406 DIGEST OF PATENTS 


254,550—Mar. 7, 1882. Thomas and Robert Hoiiipay, England. 


Process of dyeing colors on textile fabrics. Azo dyes developed on fiber, by one 
or two bath methods. 


Amino azo BENZENE, or other, is coupled on fiber with 1-NAPHTHOL, or other, by impregnat- 
ing fiber alternately with diazo compound and naphthol in alk. bath, or simultaneously, devel- 
oping color later in alkali. 


271,636—Feb. 6, 1883. Thomas Ho.iipay, England. 
Production of azo colors on cotton fabrics. Developing azo colors on textiles. 


Fiber, previously oiled and passed through a bath of 2-NAPHTHOL, or other is passed through 
a soln. of a diazo compound that has been neutralized by carbonate. 


302,791—July 29, 1884. ' Adolf Sprecer, Germany. (Hochst.) 
Fastening azo colors on yarn or textile fabrics. (Product also claimed.) To 
develop color of spirit sol. unsulfonated azo dyes on fiber. 


Fiber impregnated with bisulfite compound of azo dyes described in 302,790 Gr. VI with or 
without metallic salts (Al, Fe, Cr), then exposed to steam, alkali, or hot nitrite soln. 


306,546—Oct. 14, 1884. Adolphus SprrceL, Germany. (Hochst.) 
Manufacture of bisulphite compounds of azo coloring-matters. Bisulfite com- 
pounds of nonsulfonated alcohol soluble azo coloring matters to render them soluble in aq. 
Azo dyes are dissolved or suspended in alcohol and heated with bisulfite till sol. in aq. 


Boiled with alk. or nitrite, compounds are decomposed and azo dyes deposited. 
Note 302,790 and 303,335 Gr. VI. 


355,933—Jan. 11, 1887. Thomas Howiipay, England. 
Process of naphthol dyeing. Improved method of dyeing coupled azo dyes, using lead 
salts. 


Vegetable fiber is impregnated with soln. of basic lead acetate to produce lead oxide within 
the fiber, then steeped in dil. soap (Castile) soln., or an emulsion of Turkey Red oil, sulfonated 
or not, etc., then passed through a soln. of 1- or 2-NAPHTHOL, when it is ready for treatment 
with a diazo compound.. 

Note this is a process patent only. For product, see 355,035. 


855,935—Jan. 11, 1887. Thomas Horiipay, England. 


Naphthol-dyed fabric. Fiber prepared for developed azo colors. 

Fiber is passed through neut. soln. of lead salt, then through caustic alkali or soluble soap 
to form lead oxide or soap on the fiber, which is impregnated with soln. of 1- or 2-NAPHTHOL 
and is then ready to be developed by diazo component. 

Note 355,934 Gr. II. 


418,153—Dec. 31, 1880. F. Bayer, Germany. (Bayer.) 


Process of fixing azo dyes. Fixing direct colors on dyed or printed fiber. 

Animal or vegetable fibers, dyed or printed in the usual way with direct colors, are boiled 
in a'soln. of a metallic salt such as 5 per cent NiSO, or CuSO, and are thus rendered faster 
to soap, heat and light. Dyes containing diphenol ethers are changed in hue, while benzidin 
derivs. remain unchanged. 


439,953—Nov. 4, 1800. Robert Hotuipay, England. 
Process of producing azo colors on cotton or other vegetable fiber. Im- 

proved method of application of coupled azo dyes. 

Fiber is treated with a mixture of an oil, a PHENOL, or other, and an alkali and dried 
preparatory to subjecting it to a soln. of a diazo comp. for developing the color. 

Note 241,661, 252,317, 254,550 and 271,636. 


457,488—Aug. 11, 1891. Alfred FiscnrssER and Joseph Poxorny, Germany. (Fischesser.) 


Process of dyeins. 
Textile fibers, of all kinds, are alternately steeped in a soln. of a diazo or tetrazo comp. 
and of 2-oxy naphthoic acid (m.p. 216°) in alk. soln. Any amin or amino azo comp. may be 


used and sulfonated oils or metallic soaps as mordants with final passage of fiber through weak 


acid, are of advantage. 


an 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 407 


531,973—Jan. 1, 1805. Conrad ScurausE and Carl Scumipt, Germany. (Badische.) 
Nitrosamin compound. (Process also claimed.) Stable nitrosamin compound from 4- 
nitranilin, or 4- nitro phenyl nitrosamin for dyeing and printing. 

Diazo 4-NITRANILIN (10 per cent soln.) is added to enough cold NaOH soln. (18 per cent) 
so that mixture is strongly alk. Test for end of reaction, that is, for presence of unchanged 
diazo salt, is made by 2-naphthol reagent. Similar stable nitrosamin comps. from sulfanilic acid, 
benzidin, etc., are claimed and varying conditions for different materials are described. 

Note 531,974, 75, 76 and 77. 


531,974—Jan. 1, 1895. Conrad ScurAuBE and Carl Scumipt, Germany. (Badische.) 


Nitrosamin compound. Stable nitrosamin from tetrazo benzidin, easily converted to 
tetrazo comp. by excess acid and a trace of HNO,. May be used in printing. 
BENZIDIN in 28 per cent HCl soln., cooled to minus 5°, is tetrazotized, filt., and added 

slowly to 35 per cent NaOH, containing solid NaOH, keeping below 10°, more solid NaOH 

added and whole slowly poured into hot NaOH mixture at 160°, heating at this temp. until no ' 
reaction is given with naphthol. 
Addition to 531,973. 


531,975—Jan. 1, 1895. Conrad ScHRAUBE and Carl Scumipt, Germany. (Badische.) 
Nitrosamin compound. Stable nitrosamin compounds, easily converted by excess acid 
and trace of HNO, into diazo comps. 

Diazo comps. containing acid groups such as (a) nitramins, chlor prods., etc., are converted 
to NITROSAMINS by NaOH at ordinary temp. or (b) amino comps. without acid.substituents, are 
heated with strong alk. at 100° or above, (c) or sulfo-amino comps. are heated at intermediate 
temps. 

Note 531,973, -74, -76 and -77. 


531,976—Jan. 1, 1805. Conrad ScHRAUBE and Carl Scumipt, Germany. (Badische.) 
Nitrosamin compound. Stable nitrosamin compound, which with excess acid and trace 

HNO, form diazo comp. 

I- OF 2-NAPHTHYLAMIN is diazotized and 10-12 per cent soln. thereof added to 35 per cent 
NaOH, and powdered NaOH also added while temp. is kept below 5°. The mixture is then 
poured into strong NaOH at 150° and kept at this temp. till all is converted. 

Note 531,973, -74, -75, and -77. 


531,977—Jan. 1, 18095. Conrad Scurause and Carl Scumipt, Germany. (Badische.) 
Nitrosamin compound. Stable nitrosamin compound. 
D1ANISIDIN, tetrazotized, is added below 10° to 35 per cent NaOH containing solid NaOH, 


more NaOH added and mixture gradually poured into hot NaOH at 140-150°. 
Addition to 531,973, -74, -75, and -76. 


560,890—May 26, 1896. Edward BroEMME, Russia. 
Process of producing lakes. Dyestuff lakes for printing from azo dyes, (mono, dis, 
etc.), vegetable colors, basic triphenylmethane dyes, etc. 

Ponceau R is dissolved in aq. sod. carb. soln. to which is added aluminum sulfate (free of 
Fe) and then SrCl,, (from strontianite and HCl). Or xyuip1n is coupled with 2-NAPHTHOL in 
alk. Na,CO, soln. containing SrCl,. Ljists of dyes that may be used are given. Patent claims 
superiority of strontium over barium as lake-base, also recommends sulfate instead of carbonate. 


575,228—Jan. 12, 1897. Moritz von Gatiois, Germany. (Hochst.) 
Stable diazo compound. (Process also claimed.) 4-Nitro diazo benzol sulfate or other 

stable diazo salts, non-explosive. 

4-NITRANILIN or dianisidin diazotized in conc. aq. soln. with large excess (50 per cent) 
mineral acid is stable at higher temps. (45°) and may be evaporated to paste, which when mixed 
with equal weight of anhyd. Na,SO,, calcined alum, acid Al or Zn sulfate and dried to powder 
below 45°, best in vacuum, is stable and non-explosive. 

S. 408—“Dianisidin Blue.” Classed by Schulz as dye. 


408 DIGEST OF PATENTS 


582,853—May 18, 1897. Adolf Frrr, Germany. 


Stable diazo compound. (Process also claimed.) Disulfo naphthalene diazo 4-nitr- 
anilin, a stable diazo comp. ready for dyeing and printing azo dyes. 
4-NITRANILIN, 2 mols. or other aromatic amino comp., is dissolved in equal parts (66°) 
H,SO,, nitrite added at low temp., then mixture added to NAPHTHALENE disulfo, or other, and 
dried at 30-40°. Other components claimed and application of product to cloth prepared with 
2-naphthol. 


593,192—Nov. 9, 1897. Victor G. Biorpt, Maryland. 
Process of dyeing. Improved and more economical method of dyeing coupled azo dyes. 

Goods are impregnated with soln. of the primulin or diamin series of colors, or logwood 
or other vegetable dye capable of diazotization, and subjected to action of nitrous acid gas, 
alone or associated with air, steam or other gases, instead of in the usual aq. soln. Nitrous 
acid fumes may be made in one of several ways described. 


595,894—Dec. 21, 1897. Herman SrtypertuH and Moritz von Gatiois, Germany. (Héchst.) 
Process of producing diazonaphthalene on fiber. Stable form of 1-naphthylamin, 
that may be readily diazotized on fiber. 


I-NAPHTHYLAMIN is cofiverted to the sulfate and the latter ground to fine powd. When 
made into paste with ice, and nitrite, this powder is quantitatively diazotized. 


598,118—Feb. 1, 1808. H. Scumip, Germany. (Hochst.) 


Process of discharging red. (Product also claimed.) Discharging Paranitranilin Red, 
or other azo dye. 
A discharging color containing tin salt and acetin, etc., having solvent action on Red, is 
printed on the Paranitranilin Red, and steamed. 
S. 56—‘‘Paranitranilin Red.” 


601,420—Mar. 29, 1808. H. Zozsnin and A. Kinec, Germany. 
Process of discharge printing. Discharge printing on Paranitranilin Red. 

Fabric impregnated with 2-NAPHTHOL, sodium salt, is passed through bath of diazo 4-N1TRAN- 
ILIN, washed, soaped, dried, imnregnated on one or both sides with glucose or sugar, etc., dried 
and printed with a strong alk. discharge color containing glucose or glycerin, etc., and gum. 
Besides WHITE, also VARI-COLORED dyes can be printed by mixing appropriate colors with dis- 
charge. 


623,697—Apr. 25, 1899. M. Becxe and A. Beit, Germany. (Héchst.) 
Process of dyeing unions. 

Basic disazo dyes linked by at least three aromatic residues and containing an aromatic 
ammonium base fix easily on wool and cotton from acid bath. The strong basic character of 
dye must be retained. Long lists of components are claimed, and detailed methods of applica- 


tion and formulas given. 
S. 222—‘Janus Yellow GR,” S. 240—“Janus Red B,” S. 435—“Janus Brown B.” Schulz 
classes this patent as a dye. 


647,268—Apr. 10, 1900. Friedrich Just, Germany. (Hochst.) 
Process of dyeing. Chromating dyes in presence of reducing agent to more completely 
fix the dye. 


Fiber dyed with Chrome Brown RO, Chromotrope §S, or similar dye, is boiled in bichromate 
soln. containing H,SO, and lactic acid (0.5 wt. of bichrom.) or lactate, tartaric or citric acids 
or their salts, bisulfite, etc. 


657,767—Sept. 11, 1900. Eugen Grossman, Switzerland. (Geigy.) 
- Naphthol prepared with rosin soap. (Process, not product, claimed.) Coupling azo 
dyes on fiber in presence of rosin soap as mordant. 
Fiber is impregnated with a phenol and a soap or sod. salt of abietinic acid (obtained by 
heating NaOH with colophony, which is cheaper than Turkey-Red oil), castor oil or olive oil 
soap, tragacanth and gelatin or gum. 


ee Cee ee ee | 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL, 409 


711,953—Oct. 28, 1902. Carl Encau, Germany. (Cassella.) 
Process of dyeing acid colors. Dyeing with azo dyes on mixed fibers colors similar 
to logwood black by employing tannin lakes. | 


Dye bath contains 4 per cent NaAPpHTHYL Blue Black N, with 15 per cent sumac extract 
(30°), 2-3 per cent oxalic acid, and when dye is nearly exhausted 3 per cent CuSO, and 6 per 
cent FeSO, are added. Dyeings are uniform, of good luster, strong feel, and take a good finish. 


725,847—Apr. 21, 1903. Myrtil Kaun, Germany. (Oehler.) 
Process of dyeing. Oxidizing azo dyes on fiber with CrO,. 

Fiber is treated in bath containing 3-6 per cent H,SO, and 1o per cent Glauber’s, with 6 
per cent of an azo dye derived from ortho amino PHENOL or its derivs. coupled with 1.5-dioxy 
naphthalene, such as 2-amino phenol 4-sulfo azo 1.5-dioxy naphthalene. The resulting red violet 
shade is changed to deep black by boiling dyed wool one half hour in bath of 3-4 per cent 
K,Cr,O,, and 3-6 per cent H,SO,. Old dye bath may be used without additional H,SO,. List 
of other dyes that may be used is given. 


%741,029—Oct. 13, 1903. Richard Grey and Otto Sresert, Germany. (Berlin.) 
Red azo lake. ' 
4-TOLUIDIN 2-sulfo azo 3-oxy NAPHTHOIC acid is pptd. on metallic bases, Ca, Ba, Al, Zn. 


Rep lakes for lithographic inks, fast to water, oil, light. 
S. 152—“Lithol Rubin B.” For dye, sec 743,071. Gr. VI. 


761,310—May 31, 1904. Walther Logs, Germany. (Boehringer.) 
Preparation of azo dyes. Azo dyes produced by electric current. 

An amin, a nitrite and an acid coupling agent are dissolved in the same bath and an electric 
current of 0.5-7.5 amps. per sq. dcm. at 40-90° is passed, using diaphragm, Pt anode, cathode 
of any metal, caustic alk. in the cathode chamber, and the azo dye components in the anode 
chamber. The coupling agent must be unaffected by HNO,. 


778,175—Dec. 20, 1904. Leopold H. DEHorF and Gustav WESsBECHER, Germany. (Badische.) 
Compound dye. A dye mixture which after chroming on fiber is fast to acids, washing, 
milling and light. 

Palatin Chrome Black from 2.6-dichlor 3.5-diamino PHENOL 4-sulfo disazo 2-NAPHTHOL, of 
t-naphthylamin 2.4-disulfo azo 2-naphthol, or other ortho oxy azo 2-naphthol comp., 2.5 parts, 
is mixed with 1.5 parts ALKALI vioLET 4 BN or other substituted rosanilin sulfo comp. and suit- 
able salts as diluents. Method of dyeing given. 

Note 667,935 Gr. VI. 


793,743—July 4, 1905. Traugott SANDMEYER, Switzerland. (Geigy.) 
Process of making diazo compounds. Stable diazo comps. of amino naphthols. 


1-Amino 2-NAPHTHOL 4-sulfo, or other, is diazotized without acid by nitrite in aq. soln. with 
copper or other metallic salt as catalyst. 


794,314—July 11, 1905. Bernhard Ricuarp, Switzerland. (Geigy.) 
Process of dyeing. Fixing and developing azo dyes with CuS0O,. 

Wool fiber is immersed in 5 per cent acetic acid and 2 per cent 2-amino 4-crESOL 6-sulfo 
azo ethyl 1-NAPHTHYLAMIN, or other azo dye from ortho amino phenol derivs. and 1-naphthyl- 
amin, boiled 45-60 m., then 2 per cent CuSO, added and boiled 30 m. The original violet-red 
shade is changed to violet-blue. 


795,058—July 18, 1905. Alexander Orto, Germany. (Hochst.) 
Bisulfite compound of a tetrazo dye and process of making same. Stable 

bisulfite compounds of ortho disazo dyes. 

2.6-Diamino PHENOL 4-sulfo is tetrazotized, coupled with 2 mols. 2-NAPHTHOL, heated with 
bisulfite till dissolved, made just acid with H,SO, and dried. 

Note 665,696 Gr. VI. 


799,058—Sept. 12, 1905. Carl IMMERHEISER, Germany. (Badische.) 
Azo-dye lake and process of making same. Yellow to red dye lakes from azo 
dyes and mixtures. 


410 DIGEST OF PATENTS 


Xyuiwin, either crude or purified, or other, is coupled with 4-crEsoL, forming an azo dye 
that is soft or liquid at ordinary temps., warmed and intimately mixed with finely ground heavy 
spar, kaolin, BaCl,, etc. Mixtures with other dye comps. can be made. 


842,560—Jan. 29, 1907. Richard KircuHorr, Germany. (Berlin.) 
Orange lake and process of making same. Orange lakes from azo dyes. 

SuLFANILIC acid azo 2-nitro PHENOL, or other, is converted into lake of alk. earth or other 
suitable metal by mixing with oxide, hydroxide or salt of Ba, Sr, Mg, Ca, etc., using CaSO,, 
Al(OH), or the like as substratum. 


872,181—Nov. 26, 1907. Carl IMMERHEISER, Germany. (Badische.) 
Process of making red lakes. Forming dry red azo dye lakes. 


I-NAPHTHALENE sulfo azo 2-NAPHTHOL, or ‘‘Lithol Red,’’ is ground together with a sub- 
stratum, a metallic compound (BaCl,) and limited amount of water (less than 10 per cent) to 
form practically dry lake. 


890,254—June 9, 1908. Ernst Uuricus, Germany. (Wilfing.) 


Process of making lakes. Making lakes for wall-papers, painters, printers and lithog- 
taphers from azo dyes containing sulfo groups. 
Azo dye lakes with BaCl, are pptd. in usual manner, dried and ground with dry gypsum, 
heavy spar, etc., which should be added gradually. Advantages of new process enumerated, the 
most important being a saving in cost of evaporation, apparatus, etc. 


910,030—Jan. 19, 19009. Ernst Uxnricus, Germany. (Wilfing.) 
Azo lake and process of making same. (Product not claimed.) Azo lakes pptd., 
without alkali, sulfo groups being previously united to metallic constituents. 

SULFANILIC acid is boiled in aq. soln. with BaCO, to form Ba salt, diazotized and coupled 
with 2-NAPHTHOL in acid soln. of 50 per cent Turkey-Red oi] then Al(OH), added. Other com- 
ponents and examples given and claims for superiority made. 

S. 145—“Orange II.”” Note 911,186 Gr. VI and 918,244 for related comps. 


913,633—Feb. 23, 19009. Emile A. FournEaux, England. (Badische.) 


Process of obtaining paranitranilin red, ete. Printing or dyeing paranitranilin 
red, or other. 
Fiber is prepared with alk. 2-NAPHTHOL soln. containing ACETIN, etc., and printed or dyed 


with soln. of NITROSAMIN RED and acetin, or other, to neutralize injurious excess of alkali gen- 
erated by reaction. 


913,634—Feb. 23, 1900. Emile A. FournEAux, England. (Badische.) 
Process of obtaining Paranitranilin Red, ete. Producing Paranitranilin Red on 
fiber directly. 

Solns. of basic Mg. salt of 2-NAPHTHOL 1-sulfo and of NITROSAMIN RED together with salt 
of Mg., gum, castor oil, acid, turpentine, ACETIN, etc., and a little UREA, are mixed, printed on 
fiber and developed by steam, etc. Sulfo group of naphthol is split off and is replaced by 
diazo coupling. . 

Note 531,974 to 77. 


918,244—Apr. 13, 1900. Emil WvurtHNerR, Germany. (Siegle.) 
Lake from sulfonated azo dyes. (Process, not product, claimed.) Lakes from sul- 
fonated azo dyes by adding metallic salts before formation of dye. 


2-NAPHTHYLAMIN 1-sulfo is diazotized, BaCl, added to form salt, then coupled with 2- 
NAPHTHOL,. 
Note 910,030 and 911,186 Gr. VI for similar comps. 


936,260—Oct. 5, 1909. Ernst Uuricus, Germany. (Wiulfing.) 
Process of making a red azo dye. “F-anhydride” or anhydrous Lithol Red, a stable 
comp. 


2-NAPHTHYLAMIN 1-Sulfo is coupled at 60°, with or without neutral salt, with 2-NAPHTHOL, 
high temp. of coupling causing the formation of an anhydride. 
S. 173—‘‘Lithol Red R.” Note 650,757 Gr. VI. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL, Aid 


937,741—Oct. 19, 1909. Ernst Uxricus, Germany. (Wiilfing.) 
Azo dye. (Process also claimed.) ‘‘F-anhydride,” a condensation product of two mols. Lithol 
Red R by elimination of H,O from naphthols. 


2-NAPHTHYLAMIN 1-sulfo azo 2-NAPHTHOL is dried and heated in acEric anhyd. 
S. 175—“‘Lithol Red R.”’ 


972,130—Oct. 4, 1910. Friedrich RunxkeL and Martin Herzperc, Germany. (Bayer.) 
Pigment-color. Red lakes fast to light and oil. 
1-NAPHTHYLAMIN azO I-NAPHTHOL 5-sulfo is pptd. as dye lake with BaCl, or finished dye 


mixed in aq. with heavy spar, filt., dried and well ground. 
_S. 108—‘‘Double Ponceau R,”’ etc. 


976,219—Nov. 22, 1910. Georg Rupo_pH, Germany. (Bayer.) 
Process of dyeing half-woolen goods. Dyeing mixed cotton and wool in one bath. 
A dye bath for half wool goods is prepared with one or more direct azo dyes, Glauber’s salt, 


acetic acid and at 70° just before entering goods bichromate is added, and bath boiled 1.5-2 
hours. Both wool and cotton fiber are dyed at same time in one bath. 


1,057,137—Mar. 25, 1913. Richard Fiscuer, Germany. (Bayer.) 
Producing stable solutions of diazotized nitranilins. (Product also claimed.) 

Stable solns. of diazo nitranilins for dyeing and printing. 

Stable dyeing medium is obtained by adding to solns. and pastes containing NITRANILINS 
before diazotizing an aromatic sulfonic acid in quantity not sufficient for formation of neutral 
salt. NAPHTHALENE TRISULFO, about %4 to % weight of nitranilin, specially claimed. 

S. 56—‘‘Paranitranilin Red,” etc. 


1,060,097—Apr. 29, 1913. Myrtil Kaun and Anton OssENBECK, Germany. (Bayer.) 
Dye-bath. Dyeing by one-bath method. 

Dye bath is prepared with 4 per cent dye from 6-chlor 4-nitro 2-amino PHENOL, coupled with 
2-NAPHTHOL, boiled, 2 per cent bichromate added, wool entered at 60-80°, boiled for 45 min., 
2-3 per cent acetic acid added slowly and boiled 1.5 hours longer. Brown to BLAck acid dyes, 
fast to light, fulling and rubbing, are produced. Other unsulfonated azo dyes from nitro amino 
phenols are claimed. ; 


1,077,655—Nov. 4; 1913. Ernst Unricus, Russia. (Badische.) 
Azo coloring matter. 2-NAPHTHYLAMIN 1-Sulfo azo 2-NAPHTHOL, bisulfite comp., suited for 
production of color lakes. 
Sodium salt or free acid of Lithol Red R heated at 80—90° in dil. bisulfite soln., and salted 


out. Product is an orange powd. easily sol. in aq. from which soln. the dye is pptd. by NaOH. 
S. 173—“Lithol Red R.” 


1,093,567—Apr. 14, 1914. Otto N. Wirt, Germany. (Berlin.) 
Stable nitrobenzene-diazonium derivatives. Stable, neutral, double salts of naph- 
thalene sulfo, Na salt, and nitrobenzene diazonium deriv. 
Diazo 4-nitro BENZENE chloride in HCl soln., mixed with 2 mols. free NAPHTHALENE 2-sulfo. 
Other components claimed. Products require no acid or neut. agent for dye baths and. print 


colors. 
Note 582,853. 


1,096,198—May 12, 1914. Leopold ScnuutzE and Robert FiscuEer, Germany. 
Printing-colors. Printing pastes for engraving. 

Ba lake of Naphthol Black or other lake or mixture, is ground in paste composed of Na,CO,, 
albumen, sodium sulfricinoleate, refined rosin oil or turpentine oil, and water. KOH can be 
used instead of Na,CO,. Resulting printing pastes have special properties indicated by patent. 


1,099,108—June 2, 1914. Adolf Wintuer, August L. Lasxa, Arthur Z1TscHER, 
Felix Kunert and Edwin Acker, Germany. (Griesheim.) 
Producing ice colors. 
Cotton goods are impregnated with soln. of an aryl amin of 2.3-oxy NAPHTHOIC acid and 
without drying are passed through a nonsulfonated diazo comp. derived from 2-ANISIDIN or other. 
Note 1,034,853 and 1,042,356 Gr. VI. 
27 


412 DIGEST OF PATENTS 


1,127,027—Feb. 2, 1915. Felix Kunert and Edwin Acker, Germany. (Griesheim.) 
Process of producing dyestuffs on the fiber by means of the one-bath 

method. Dyeing on fiber by one-bath method. 

2-Oxy 3-NAPHTHOIC acid anilid in NaOH soln. (35°) containing sodium ricinoleate, is dis- 
solved in hot aq., cooled, and added to soln. of nitrosamin alkali salt of 4-NITRANILIN, and thick- 
ening agent. Goods are printed, dried, and passed at 80° through 2 per cent bichromate soln. 
Other components claimed. 

Note 1,099,108 Gr. VI and 913,634. 


1,169,267—Jan. 25, 1916. Felix Kunert, Germany. (Griesheim.) 
Dyeing artificial silk. Developed azo dyes on viscose or other artificial silk. 

Silk is passed through aq. at 60° then impregnated with 2-oxy 3-NAPHTHOIC acid anilid or 
derivs. at 30-40°, centrifuged, cooled, and without drying is placed in acetic soln. of diazo 
4-nitro 2-TOLUIDIN or deriv. not containing a sulfo group. Numerous examples given of com- 
binations of different components for varying depths of shade. 


1,193,566—Aug. 8, 1916. Felix Kunert, Germany. (Griesheim.) 
Compounds for use in the production of dyestuffs. Stable nitrosamin compounds 

ready for printing. 

2-Oxy 3-NAPHTHOIC acid anilid, or other, is ground in NaOH soln. (35°), heated till 
naphtholate is formed, then alk. paste of alk. salt of nitrosamin from 2-nitro 4-roLuipiIn added 
in ball mill, Variations in method, and other components are claimed. 

Addition to 1,127,027. 


1,200,726—Oct. 10, 1916. Martin Hanxet, Germany. (Griesheim.) 
Process for the manufacture of alkali salts of nitrosamins of primary aro- 
matic amins. Alkali salts of stable nitrosamins of primary amins. 
2-DIANISIDIN is coupled with 2 mols. NAPHTHALENE 1.5-disulfo, dried, product ground with 
NaOH, a limited amount of ag. added and mass heated until test sample will not couple with 
2-naphthol. 


1,213,608—Jan. 23, 1917. 
Gadient Ener, Armin Gros and Fritz Straus, Switzerland. (Basle.) 
Green chromium compound and a process of making same. To form a soluble 
green chromium azo dye compound, fast to light, for animal fibers. 


4-Nitro 2-amino PHENOL azO I-AMINO 8-NAPHTHOL 3.6-disulfo, “Chromium Fast Green G,” 
is boiled in aq. with chromium salts and green dye pptd. and purified from accompanying red 
component by salting out. Dyeings are of purer shade than those of original color after 
chromating on fiber. 


1,274,047—July 30, 1918. Charles C. Hurrman, Illinois. (Sunbeam.) 


Universal yellow dye and method of producing the same. Alkali proof soap 2 
dyes for all fibers from any type dye or from mixtures. 


CurysompIn or other basic, acid or neutral dye of azo class, in boiling aq. is added to 
soap soln. containing excess alkali, before saponification is complete, a definite chemical compound 
being formed between dye and soap (fatty acid). 


1,274,048—July 30, 1918. Charles C. Hurrman, Illinois. (Sunbeam.) J 


Universal brown dye and method of producing the same. Brown soap dye, — 
alkali proof. é 


Process and claims are same as 1,274,047, using several dyes, such as Acid Red, Chrysoidin — 
Yellow, Direct Black and Methylene Blue, product separated, dissolved in hot aq. and added in 
order mentioned to soap comp., time being allowed between successive additions to avoid pptn. 


1,310,518—July 22, 1910. Wm. A. Arnswortu, Michigan. (Mather, %.) : 


Dyeing composition. Composition for dyeing yarn without boiling. 


4 


er 


Dye compound contains 3 oz. powd. dye, thoroughly incorporated with 5 parts glycerin, — 
diluted with 6 gals. alcohol and a little aq. Yarn, etc. in this soln. will absorb dye instantly 
without application of heat, and fiber dries quickly. 4 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 413 


1,315,961—Sept. 16, 1919. Charles C. HurrMan, Illinois. (Sunbeam.) 
Universal gray dye and method of producing the same. Alkali proof dye of 
gray shade. © 


Process and claims are similar to 1,274,047-8, except that a black dye, Pheno Black, is 
used in soap comp. in limited quantity so as to produce a gray shade. 


1,333,807—Mar. 16, 1920. John IL. Kang, Pennsylvania. 


Production of azo dyes. (Product also claimed.) Improved azo dyes by using starch 
in coupling bath. 


ANILIN, or other aromatic amin, is diazotized in a 1 per cent starch paste soln. -and coupled 
by pouring slowly into a dil. soln. of 3-PHENYLENE DIAMIN or other amino or diamino comp., or 
deriv. Paste from any starch may be used and quantity varied. Resulting dyes are darker in 
shade, more brilliant and purer in tone than when no starch paste is used. 


1,358,007—Nov. 9, 1920. Arthur Linz, New York. ' (Ultro.) 
Colors. (Process also claimed.) Azo dye lakes. 


5-Nitro 2-ToLUIDIN, Na salt, is coupled in aq. soln. with 2-NAPHTHOL 3.6-disulfo in presence 
of BaCl,, boiled, separated, etc., and mixed with substratum of BaSO,, Al(OH),, CaCO,, CaSO,, 
etc. Comp. of any multivalent metal may be used instead of BaCl,. 


1,417,869—May 30, 1922. Hans Torerrer, New York. (Grasselli.) 
Process of dyeing. Mordanting azo dyes with cobalt. 


Wool is dyed in usual way with azo dye from picrAmic acid coupled with NAPHTHIONIC 
acid, then boiled with 5 parts Glauber’s salt in one part acetic acid soln., 0.5 part H,SO, added 
to exhaust bath and one part cobalt sulfate, chloride or acetate, and bath boiled 30 mins. 
Or goods may first be mordanted with Co and then dyed, or meta chrome process used. One 
component of azo color should be ortho amino phenol with one or more nitro groups in same 
nucleus. 

Note 843,077, 936,321 and 1,159,375 Gr. VI. 


1,426,299—Aug. 15, 1922. Felix Kunert and Edwin Acker, Germany. (Chem. Found.) 
Multicolor printing. Using nitrosamin colors in multicolor printing. 
Nitrosamin colors to'which have been added normal chromates or other metal salts such 


as aluminum borate or sod. vanadate, form lakes capable of resisting steam and can be used 
in indigo color discharge or other effects. Formulas are given. 


1,440,566—Jan. 2, 1923. Fritz Straus, Switzerland. (Basle.) 
Process for the manufacture of chromed dyestuffs. Chromium comps. of azo dyes. 


To an aqueous suspension or paste of Cr(OH), below 70°, is added excess KOH and 
GLYCERIN or other organic comp. containing more than one hydroxyl group (polyvalent alcohols 
and phenols, tannins saccharides, derivs. of cellulose, lignins, etc.), and a chromable azo dye 
such as 1-amino 2-naphthol 4-sulfo azo 2-naphthol or 2-amino 4-chlor phenol 5-sulfo azo phenyl 
methyl pyrazolone, etc., is boiled with the potassium glycerin chromate thus formed, bath 
neut. with acid and dye salted out. 


SUBGROUP VII.—INDIGO AND INDIGOID. (In.) 


83,182—Oct. 20, 1868. John Licutrroot, England. 
Improvement in printing certain textile fabrics and yarns. Printing with in- 
digo together with mordants. 


Inpico is reduced by limited amount of SnCl, so that no excess of tin salt on fiber may 
form lake and spoil shade. Fiber is then printed by this indigotine paste together with Fe or Al 
mordant and both fixed by soln. of silicate or carbonate of alk. 


83,182—Oct. 20, 1868. Re. 3,647—Sept. 28, 1869. John Licurroot. (Amer. Print.) 


Improvement in printing certain textile fabrics and yarns. Improvement in 
printing blue or green with indigo and mordants. 


Inpico is reduced in alk. soln. with SnCl, or other, avoiding excess Sn., leuco dye pptd. by 
acid (acetic preferably), mixed with thickener, then with usual Al or Fe mordant and printed 
on cotton, linen, etc., aged, passed through soln. of alkali silicate (8°Tw) or carbonate, exposed 
to air, passed through bichromate at 39°, again ‘“‘dunged,” then dyed with madder or other, and 
finally cleared with Ca (OCI),. 


414 DIGEST OF PATENTS 


86,047—Jan. 10, 1869. Theodore Weser, Illinois. (Sargent.) 
Improved indigo dye. Improved dyeing compound of indigo. 


Hydrated protoxide of tin prepared from SnCl, and soda ash, well washed, is added to soln. 
of INDIGO in caustic alkali (from quicklime and soda) heated, and when cooled is ready for use. 
Process is in several stages that may be regulated better than usual fermentation process. 


126,663—May 14, 1872. Theodore T. Wooprurf, Pennsylvania. (Morris.) 
Improvement in processes and apparatus for the manufacture of indigo. 
Precipitation of indigo from freshly fermented extracts. 


Freshly prepared INDIGO extract is oxidized by current of air forced by pumps, the descrip- 
tion and drawings of apparatus being given. : 


126,664—May 14, 1872. Theodore T. Wooprurfr, Pennsylvania. (Morris.) 
Improvement in process and apparatus for the manufacttre of indigo. Dry- 
ing of freshly pptd. indigo. 


InpDIGO magma or paste, freshly oxidized, is drained and dried in thin strata on draining 
cloths on trays in chamber thru which strong current of warm or cold air is passed. Drawings 
of apparatus are given. 


175,829—Apr. 11, 1876. William H. Fisu, Rhode Island. 
Improvement in dyes. Indigo solution ready for vat dyeing of cotton, wool, silk, etc. 


INDIGO 16 parts, zinc dust 6 parts, sodium bisulfite 6 parts, and alkali 16 parts, are mixed 
thoroughly with 6 parts aq. and heated to 60°. Resulting paste is diluted and SnCl, added for 
dye vat. Function of each ingredient in mixture 1s explained. 


179,939—July 18, 1876. Gustav Moxt, Massachusetts. 
Improvement in blue dyes. Indigo compound ready for vat dyeing of cotton or mixtures. 


INpIGO 1 part, to 2 parts KOH in aq. soln. is heated to boiling and ‘‘Oxalere,’’* liquid 
ammonia and NH,Cl added, or mixture is made without oxalere which, shipped in separate 
package, is added as required. 


220,638—Oct. 14, 1879. Gustav Mott, Massachusetts. 
Improvement in compound dyes. Indigo dye paste ready to use when diluted and 
heated. 


Inpico XX, caustic soda, tin crystals and a syrup (made by boiling hops, madder, bran and 
molasses in water, allowing to settle and pouring off clear liquor) are mixed and boiled till 
indigo is reduced, then barreled. 

Addition to 179,939. Proportions for various uses and dye methods are given. 


235,488—Dec. 14, 1880. Adolf Baryer, Germany. (Badische.) 
Manufacture of dyestuff or coloring matter. (Product also claimed.) Improved 

indigo dyestuff from 2-nitro phenyl propiolic acid. 

Crude Indigo G, made as in 235,193, is exhausted with aq. SO,, or other reducing agent, 
filt. and dye pptd. by acid, preferably using heat. 

Note 227,470, 235,193 Gr. VII and for application of dye to fibers see 240,360. 


240,360—Apr. 109, 1881. Adolf Baryrer and Heinrich Caro, Germany. (Badische.) 
Dyeing fabrics with artificial indigo-blue. (Product also claimed.) Printing, mark- 
ing or dyeing fibers with indigo of 227,470 Gr. VII. 


2-Nitro phenyl propionic acid, alkali carbonate, starch paste and sodium xanthate mixture 
are printed on fiber and color developed at 20-50°. No steam or heat is required. Either the 
xanthate or propiolic acid may be applied to fiber separately and the other part of mixture 
printed thereon. For dyeing, the fiber is impregnated with above mixture and developed or aged 
in air. 

Addition to 227,470 and 228,300 Gr. VII. 


240,361—Apr. 19, 1881. Adolphus Batyrer, Germany. (Badische.) 
Mantfacture of artificial indigo. (Product also claimed.) Leuco indigo carmine 
compound, i 


* “Oxalere,’? a commercial product, is said to be made of zinc which is meited till fuming 
ceases, then washed, dried, triturated. See 220,638. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 415 


Indigo prepared as in 235,198, is exhausted repeatedly with cold aq. SO, or bisulfite soln. 
filtered and soln. pptd. by salt. Upon treatment with acid, dye gives off SO, and forms leuco 
indigo carmine. — 

Addition to 235,193 Gr. VII, see also 235,488. 


301,475—July 8, 1884. John BracewE.t, Massachusetts. 
Process of printing indigo colors. 

Inpico ground with alkali and water for stock soln., is mixed with dextrin or gum, heated 
to 49° and printed on fabric which has previously been impregnated with glucose, dried quickly, 
and just before printing has been steamed on the surface to break down the sugar crystals at 


the surface only. An even color on the surface of the fiber without penetrating beyond the 
surface is produced. 


305,312—Sept. 16, 1884. David Jamixgson, Maine. 


Process of dyeing black. Dyeing fast colors, black, drab, slate, on cotton, linen, jute, 
or silk, with indigo and cutch or gambier. 


Fabric is dyed with indigo in cold lime and copperas vat, then dipped in soln. of cutch o1 
gambier, adding CuSO, as fixer or mordant, then passed thru soln. of bichrom. Order can be 
reversed. 


386,933—July 31, 1888. Frederich EF. ScumittcKert, Germany. 


Process of preparing a solution of indigo for dyeing purposes. Preparation 
of leuco indigo dye vat. 


Woad bath for 1np1Go dyeing is prepared by mixing guano salts with aq. zinc dust and indigo, 
or other bodies having affinity for oxygen, and heating to 65-75°. 


888,703—Aug. 28, 1888. P. P. Micuea, Canary Islands. 


Treating plants containing indican. Method to produce more abundant yield of in- 
digo from natural indigo vat. 


During process of oxidizing indigo, nitrate or nitrite of ammonia is added to vat liquor to 
accelerate action of alkalies and act on gluten of plant. Addition of ozonized air is also 
claimed and improvements in form of vat described, with drawings. 


411,149—Sept. 17, 1880. Daniel Edouard Hucuenin, Switzerland. (Durand.) 
Blue dye. Compound of indigo and indophenol to reduce cost of dyeing. 


InpIGo and INDOPHENOL are ground together in paste and a reducing agent added, such as 
Zn, sod. bisulfite, tin salt, etc. and NaOH. Fiber, after dyeing, is oxidized in soln. of bichromate 
or other oxidizing agent, to intensify color. For manufacture of indophenol, see 261,518 and 
263,341 Gr. VIII. 


437,638—Sept. 30, 1890. Arthur AsHwortH, England. 
Indigo solution. (Process also claimed.) Preparing leuco indigo vat. 


Soln. of sod. bisulfite, 33 per cent, containing as much Zn dust, Fe or Cu, filings as it will 
dissolve, is filt, Na,S added until fully pptd., filt, and more or less NaOH added according to 
desired rate of oxidation in subsequent dyeing, more giving slower development. Ground 
INDIGO when added to above vat is immediately reduced. 


472,267—Apr. 5, 18092. FE. MicuarEztis and C. Henninc, Germany. 
Process of dyeing. Dyeing with indigo. 


Sodium bisulfite is treated with Zn, the resulting acid soln. poured off, made alk. and indigo 
white added. After dyeing in this soln., goods are passed into oxygenated water containing 
H,O, and alc. or ether, etc., to increase percentage of oxygen. 


522,042—June 26, 1894. Andre BLancHon and Augustin ALLEcRET, France. 
Process of printing indigo. Printing Indigo. 

InpIco mixed with thickening substance is printed on fiber and passed thru redutCting bath 
of bisulfite, then oxidized. 
534,560—Feb. 19, 1895. Karl Heumann, Switzerland. (Badische.) 


Artificial indigo white. Leuco indigo in powd. form intimately mixed with alkali, ready 
to apply in vat. 


416 DIGEST OF PATENTS 


ANTHRANILIC acid is condensed with chlor acrric acid by refluxing in aq. soln., product 
heated above 200° with excess caustic alkali, or alkali earth, to produce phenyl glycocol 2-carbo 
acid, melt cooled and ground to powder. 


559,163—Apr. 28, 1808. Emilio Casrati, Italy. 
Process of dyeing with indigo. Saving indigo in dye vat. 


For the purpose of economizing indigo, goods are printed with a fine network of anilin 
black before or after treatment in the indigo bath. 


657,307—Sept. 4, 1900. Max Razien, Germany. (Badische.) 
Indigo-white compound and process of making same. Stable compound of leuco 
indigo. 


Inp1co white is dissolved in 10 parts acetone, aq. or alc. to which 1 part NaOH has been 
added, and PHOSGENE gas passed in at low temp. Product is powder stable in air, dissolves in 
warm dil. NaOH to form indigo white, is diff sol. or insol. in most ordinary solvents, sol. in 
boiling acetone, heated in conc. sulf. and poured into aq. yields blue soln. 


657,320—Sept. 4, 1900. Armand J. SrrecELMANN, Germany. (Badische.) 
Stable indigo-white and process of making same. Hydroxy methylene indigo 
white or stable compound of leuco indigo. 

INDIGO WHITE is heated in neutral aq. or alc. soln. or suspension with equal part 
FORMALDEHYDE (40 per cent), at ordinary temp., the greenish ppt. filt., and dried without ex- 
clusion of air. Product, which is hydroxy methylene leuco indigc comp., is stable in air, diff. 
sol. aq. and alc., insol. ether and C,H,, easily sol. acetone and hot glac. acetic, recrystd. from 
hot alc., gives green crysts., boiled with NaOH or alk. earth yields indigo. 


671,344—Apr. 2, 1901. Rudolf Knrerscn and Paul Semper, Germany. (Badische.) 
New form of indigo readily soluble in wats and method of making same. 
Indigo sulfate, a salt of indigo, not a sulfonic acid deriv., in condition readily soluble in vat. 
Inpico, dry powder, is mixed to uniform paste in 5 parts 75 per cent sulfuric at 30° to 
form indigo sulfate without sulfonation, then diluted with 20 parts aq. and filtered. Even 
though dried, product is readily sol. 


671,994—Apr. 16, 1901. Emil Frick, Jr., Germany. 
Process of making soluble indigo paste. Indigo paste containing no alkali and large 
percentage of leuco dye. 

INDIGO is mixed with about 0.5 part zinc dust (Sn or Fe), and 25 per cent ammonia water 
gradually added. Product when pressed contains about 75 per cent indigo white. More NH, is 
required with Sn or Fe as reducing agent and resulting paste is not so rich in dye. May be 
applied to silk or in dye mixture. 


680,894—Aug. 20, 1901. : Armand J. SrreEcELMANN, Germany. (Badische.) 


Process of making indigo from indigo leuco compounds. Indigo from leuco 
comps. in presence or absence of textile fiber. 
Melt rich in INDOxYLIc acid (see E. P. 9291-1894) is dissolved in aq., nearly neut. with 
dil. H,SO,, sulfur added and warmed. Goods, worked in bath containing thiosulfate, alum and 
dil. H,SO, at 50-55° or printed with paste of gum thickening and flowers. of sulfur and 
steamed, are steeped in this indigo vat. Sulfur causes dye to oxidize quickly to deep shades, 
even in dye vat. 


690,347—Dec. 31, 1901. Wilhelm Berns, Germany. (Badische.) 


Process of discharging indigo-dyed wool. Increasing clearness of discharge effects 
on indigo dyeings by after treatment with bleaching agents. 


Indigo dyed material, printed with discharge mixture of gums and bichromate, is steamed, 
passed thru bath of oxalic acid and dil. sulf. acid, then let stand in bath of H,O, (2-3 per cent) 
containing ammonia in excess. Other bleaches than peroxide, such as gaseous or aq. SO,, 
bisulfites, percarbonates, etc., can be employed. To give colored discharge effects the gum bi- 
chromate mixture may contain Indulin (R), Methylene Blue B ext. (B) Azoflavin 3R (OY), or 
Rhodamine extra (BR), etc., or multicolored effects can be produced, all being after treated as 


described. 


4 
f 
_ 
i 
2 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL, AI7 


692,720—Feb. 4, 1902. Paul SripreL, Germany. (Badische.) 
Indigo paste. An indigo paste of 20 to 40 per cent strength that will not deposit dye. 

(a) Ten parts INDIGO paste, 4o per cent, and 5 parts 1-2 per cent gum soln. are thoroughly 
mixed and diluted to 20 per cent standard or (b) dye powder is ground with gum soln. and 


a little NaOH. Gums used may be bone, skin or fish glue, silk gum, albumen, casein, gluten, 
gelatin, starch, etc. Paste must be alkaline. 


699,033—Apr. 29, 1902. Armand J. St1EGELMANN, Germany. (Badische.) 
Process of making resist-white under indigo. Lead peroxide resist for whites under 
indigo. 


Material is printed with resist mixture containing 4 parts finely powd. PbO,, 3 parts glycerin, 
and sufficient gum water to make 10 parts, the consistency of gum water depending upon appli- 
cation. Goods are dried and dyed in indigo vat and worked at 45° in dil. HCl (containing 2 
per cent of 28-30 per cent HCl) until clear white is obtained. 


700,521—May 20, 1902. Ernesto Lurati, Germany. 
Process of fixing dyes on indigo. Printed color effects with indigo dyeings. 


Fiber is treated as a whole with a Turkey-Red oil mordant containing 2-naphthol, dried, 
printed with a diazo mixture containing material to be diazotized, nitrite, ZnSO,, Pb(Ac),, 
Pb(NO,),, white lead, kaolin and HgCl,, gum, HCl, etc., to which bichromate is added just be- 
fore use, then dyed in indigo vat and finally passed through dil. H,SO, till color develops. Any 
suitable azo dye that can be developed on the fiber may be used, or if ferro or ferricyanide of 
potassium is added to the naphthol, basic colors also may be used. 


702,730—June 17, 1902. Benno Homoixa, Germany. (Hochst.) 


Purifying raw indigo. Purification of crude synthetic or natural indigo from red-colored 
products. 
Crude INDIGO containing brown red to red colored impurities is mixed while cool with 
pyridin, or homolog, boiled some hours, filt. and indigo washed with pyridin, till washings run 
bluish, freed from pyridin by boiling in aq. then in dil. acids, dried, etc. 


710,800—Oct. 7, 1902. Fritz PETERHAUSER, Germany. (Hochst.) 


Process of dyeing indigo. Producing a leuco indigo vat that can be rendered neut. or 
acid without depositing dye and gives deep dyeing with one immersion. 

Indigo is mixed with least amount of NaOH possible for reduction, hydrosulfite mixture 
added and heated to 60° till dissolved and reduced. Material to be dyed is heated in aq. soln. 
to 50°, sufficient of above dye soln. introduced, then soln. of glue or other protein and sufficient 
sod. bisulfite at 40° added till vat is acid. Dye bath is nearly exhausted after 15 mins. 


712,246—Oct. 28, 1902. Friedrich von Boutzanon, Germany. (Hdéchst.) 


Process of making formylmethylanthranilie acid. Formyl methyl anthranilic acid 
for indigo manufacture from chlor or brom methylate of quinolin. 
Halogen methyl gu1no1in is dissolved in aq. with or without MgSO,, and to this at com- 

mon temp. a sat. soln. of KMnO, is added, the soln. filt., conc., and pptd. by HCl. Product 

forms yellowish crysts. with odor of coumarin, m.p. 167°, easily sol. in alc., in hot aq., and 
when boiled with dil. alk. gives methyl anthranilic acid. 


715,213—Dec. 2, 1902. Alexander W. Piaynet, England. (Macdonald.) 
Process of preparing indigo-vats. Reducing loss of dye in indigo vats. 


Zn is boiled in an alk. bisulfite bath and the clear liquor decanted into the vat, introducing 
the liquor well below the surface. Indigo paste (preferably containing glycerin) is mixed in a 
separate vessel with part of this vat liquor, strained, and returned to the vat which is boiled 
and cooled to 65° by cold water introduced below the surface. Vat is clear and ready for use. 
Drawings and description of apparatus are given, and a tabulation of proportions of ingredients 
for different strengths of dye. 


720,501—Feb. 10, 1903. Armand J. Sr1ecELMANN, Germany. (Badische.) 


Increasing the fastness of indigo dyeings. Increasing fastness of indigo dyeings 
to washing and chlorine by use of Turkey red oil and alumina mordant. 
Indigo dyed yarn is worked in bath of 10 per cent Turkey Red oil, dried at 50-70°, passed 
through bath of 7 per cent aluminum acetate, and again dried. 


A418 DIGEST OF PATENTS 


723,007—Mar. 17, 1903. Rudolf Miiier and Otto Scuwas. (Hochst.) 
Reducing indigo. Reducing indigo by electric current. 


InpDIGO paste, 20 per cent, 300 grams is electrolyzed at 3-5 amp. per sq. dcm. without dia- 
phragm, at 60-100°, with 415 cc. 30 per cent Na,SO,, 415 cc. sod. sulfite (10 per cent SO,) 
and 55 cc. of 40 per cent NaHSO,, using lead electrodes, for 24 amp. hours. Current and 
voltage may vary within wide limits. 


744,417—Nov. 17, 1903. Paul Semper, Germany. (Badische.) 
Light indigo powder. Fine indigo powder, that will readily reduce. 


Inpico, dry in lumps, and fairly pure, treated in disintegrator of any type (one described) 
until of lightness desired, that is, of sp. gr. 0.1 to 0.25 instead of 0.4 to 0.5, then mixed in 20 
per cent paste with aq., will not deposit dye on three months standing and will dissolve in “‘fer- 
mentation vat’ within 24 hours. Drawing and description of vat are given. 


765,590—July 19, 1904. Paul E. Oserreit, Germany. (Badische.) 
Process of purifying indigo. Purification of indigo, natural or synthetic. 


Heat finely divided rnpIGo to 200-270° until red impurities are destreyed and escape partly 
as vapor while indigo blue remains, as this temp. is below its sublimation or decomposition point. 
After boiling in HCl, filtrate should not show reddish color. 


780,8S6—Jan. 24, 1905. Rudolf Hurzier, Germany. (Badische.) 
Process of purifying indigo. 


Inpico, finely ground, is mixed with 3 parts raw phenol, a-naphthol ethyl ether, or other 
solvent, stirred and heated to 120-140°, filt. by suction, filter-pressed, washed with phenol, etc. 


794,049—July 4, 1905. Paul Serpe, and Robert Wimmer, Germany. (Badische.) 
Process of making indigo-white. lLeuco indigo produced by action of indoxyl upon 
indigo. 


Inpoxyt melt (a) dissolved in hot aq. is oxidized with limited amount of air until indigo 
begins to separate, filtered and indigo white in filtrate pptd. by CO,, (6) or dissolved at about 
90° and oxidized by equal amount of INDIGO, with or without ferrous sulfate, alk. sulfite, or 
other as catalyzer. 


794,050—July 4, 1905. Paul SELLer, Germany. (Badische.) 


Hydrosulfite indigo-vat. lLeuco indigo vat fixing 4 per cent indigo on wool by one dip 
of 20 minutes duration. 


The stock hydrosulfite is prepared by dissolving one part solid hydrosulfite in 5 parts aq., 
containing 0.5-.6 per cent NaOH and preserving out of contact with air. The stock indigo soln. 
consists of 1 part pure indigo (5 parts 20 per cent paste) mixed with 2.25 parts 18 per cent 
NaOH, 15 parts above hydrosulfite, warmed to 50° and let stand 30 min. This stock soln. is 
added to 1,000 parts dye vat containing 400 parts hydrosulfite and then 3.5 parts 10 per cent 
glue is added, wool immersed for 5 minutes and 0.6 part of NH,Cl in aq. gradually run in. 
Total time is 20 m. and temp. 50-52°. Other variations of method are described. 


ee ea ee 


803,855—Nov. 7, 1905. Julius Rissert, Germany. 


Process of dyeing indigo resists. Simpler process for printing indigo, fast to rubbing, 
with back side of fiber of different shade from face when desired. 


Fabric is impregnated with reducing paste such as glucose or dextrose (8°) and dried, and 
a resist printing paste is applied. Verdigris, CuSO, Cu(NO,),, pipe clay, FbSO,, Pb(NO,),, 
Pb(C,H,O,),, burnt starch, alum, mucilage and water, or for white resists the lead salts are 
omitted and other salts such as Mn, Ni, etc., may be used in the resist paste. Goods are dried 
and are partly or entirely padded with alk. indigo print color, again dried well, steamed for 
20-30 seconds, and developed by washing. Vats may be of continuous or plunging type. Effects 
on back and front side of goods may be varied. 


ee ee eee 


807,453—Dec. 19, 1905. John W. Fries, North Carolina. 
Indigo dye. Padding liquor for indigo dyeing. 
Inpico, dry powder, is mixed with Zn dust, solid NaOH, sifted CaO and starch in propor- 


tions of 4, 4, 2, 12, and 2 respectively and 2 parts alizarin oil if desired. Lime prepared as 
“milk of lime’? and some water are used as solvent. Advantages in use of each ingredient are © 


given. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 419 


808,398—Dec. 26, 1905. Herman Mi.uer, France. 
Process of indigo dyeing. Leuco indigo reduced by tin salt and fixed by bichromate. 


For cotton dyeing 1 part indigo is boiled in 3 parts tin acetate 20-25° (SnO, or other tin 
oxide dissolved in acetic acid) then slowly poured into 9 parts 40° NaOH and boiled till indigo 
is dissolved, then 7 parts aq. are added and soln. strained. Goods are passed through dye re- 
ceptacle in dyeing machine for 10-15 secs., well squeezed, slightly aired, and passed into a fixing 
soln. of dil. HCl and of bichromate. For silk or wool just sufficient NaOH is used to dissolve 
and reduce the indigo. 


$08,443—Dec. 26, 1905. Moritz von GatLois (Hochst.) 


Process of printing with indigo. Printing indigo by simultaneous application of dye 
and stable double compounds of aldehyde hydrosulfite and strong caustic. 

Soln. A. Twelve parts formaldehyde hydrosulfite are dissolved in 5 parts aq. at 4o0-50°, 
cooled and stirred into 50 parts alkali thickener. Soln. B. Fifteen parts 20 per cent indigo 
paste are stirred with 18 parts alkali thickener, cooled, and B stirred into A. The alkali thick- 
ener consists of 12 parts “gomme industrielle” dissolved in 43 pts. hot aq. and added cold to 45 
parts solid NaOH while stirring. Bleached cotton or that dyed with Turkey red is printed with 
above dye mixture, dried, well steamed at 90-100° and washed to develop color. 


$20,S8S69—May 15, 1906. Henry S. A. Hout, Germany. (Badische.) 

Process of making indigo coloring-matter. Preparing finely divided indigo. 
Inpoxyuic acid, indigo white, or other leuco indigo comp. in dil. NaOH soln. containing soft 

soap, Turkey-Red oil, or alkali salt of any fatty or resin acid, is oxidized by air or other agent. 


8$20,900—May 15, 1906. Robert Wimmer, Germany. (Badische.) 


Reduction of indigo coloring-matters. Preparing leuco indigo vat by cheaper pro- 
cess, using Fe. 

Alkali soln., 10° Be, (at least 614 per cent), containing finely divided Fe, is heated to 75°, 
Inp1co added and temp. maintained till reduction is complete, filt. by pump, washed, etc. A 30 
per cent soln. may be produced. Thus the metal is removed by filtration whereas after reduc- 
tion with zinc the metal remains in soln. and must be separated before dycing. 


826,428—July 17, 1906. Henry S. A. Hott and Karl Reinxinc, Germany. (Badische.) 
Process of printing indigo coloring-matter. Cheaper process for printing indigo 
by employing maltose for glucose. 

Wheat starch is boiled to paste with water, cooled, and kept at fw-70° with 2 per cent of 
“diastefor” or equivalent amount of malt extract until completely hydrolyzed (3-4 hours), di- 
luted to Sp. Gr. 1.052 and material padded therewith before printing with indigo. Inferior 
starch, such as that from rice refuse, may be used also, and maltose may be unpurified. Results 
are fully as good as when glucose is used. 


833,654—Oct. 16, 1906. Robert Wimmer, Germany. (Badische.) 
Alkali salt of indigo white and process of making same. Solid, dry, stable salts 


of leuco indigo, easily soluble in aq. 

Inpvico, reduced with iron powder in dil. NaOH soln., is filt. and evap. in vacuum at 8c—90°. 
Product, which must contain no excess of alkali to cause decomposition, may be diluted with 
CaO to contain definite percentage of dye. 

This patent apparently antedates 906,307, credited by Schulz to Schmidt. 
8$35,462—Nov..-6, 1906. Paul E. Oxperrert, Germany. (Badische.) 
Process of making halogenated indigo-white. Production of halogen indigo white, 


or homologs, without loss of halogen. 

INDIGO WHITE, or homolog, in dil. NaOH soln. is warmed to 80—-100° and brom INDIGO, or 
other halogenated indigo added. The latter is reduced by the indigo white, which 1n its turn is 
oxidized to indigo and is filtered off, and resulting bath of halogenated indigo white used direct. 

Near S. 885—‘“‘Brilliant Indigo B.” 


8$43,566—Feb. 5, 1907. i Robert Wimmer, Germany. (Badische.) 


Process of reducing indigo coloring-matters. Reducing indigo to leuco form by 


means of Fe and alkali salt, instead of caustic. . 
Inp1co, 2 parts, is mixed at 75° with 3 parts of the disodium salt of INDIGO WHITE (or with 
sodium carbonate, phosphate, sulfide, or other alkali salt in conc. soln.) and 2 parts iron powder. 


Note 820,900. 


420 DIGEST OF PATENTS 


885,978—Apr. 28, 1908. Henri Cuaumat, France. 


Preparation of the indigo-vat employed in dyeing. Electrolytic process for re- 
duction of indigo in vat. 


Cathode is molded of indigo as impalpable powd. with graphite or metallic powd. that con- 
ducts electricity. Bath of alk. or alk. earth salts is protected from air by a layer of oil or inert 
gas. Anode is of carbon or nonoxidizable metal and may be placed inside a diaphragm. Oxy- 
gen produced at the anode is removed by suction unless bath contains sulfids or sulfites. Hydro- 
gen and alkali formed at cathode, dissolve and reduce the indigo in a few hours. Pure conc. 
solns. may be preserved indefinitely out of contact with air; dyeings are uniform in shade, and 
process is economical. 


893,468—July 14, 1908. Gadient Enc1, Switzerland. (Basle.) 


Leuco compounds of wat dyes and process of making same. Leuco thio indigo 
or indirubin compounds for printing. 

Salicyl] TH10 AcETIC acid heated alone or mixed with 1saTIn a-anilid or its arylides and a 
solvent and condensing agent, such as NITRO BENZENE and ACETIC ANHYD., is halogenated, re- 
duced with KHS in alc. suspension, alc. distilled off and dye pptd. as fine crysts. by dil HCl. 
As paste, the leuco derivs. are adapted for printing. 

Note 831,844, 836,309, 841,003, 848,354, -5 and -6 (Gr. VII). 


906,307—Dec. 8, 1908. Albrecht Scumipt, Germany. (Hodchst.) 
Manufacture of indigo-white preparations suitable for fermentation-vats. 

Concentrated, stable, indigo-white preparations, especially suited for fermentation vats. 

INDIGO WHITE, homologs or halogenated derivs., containing about 75 per cent dry dye, ob- 
tained by reduction with Zn, bisulfite, hydrosulfite or electrolysis, as paste or press cake, is 
mixed with 18 to 70 per cent thick liquid molasses or other saccharine substance, further evap- 
orated in vacuum to paste or solid. Products are sol. in dil. NaOH (YG), and when oxidized 
give blue dyes, partly insol. and partly sol. in aq. as saccharides. 


910,889—Jan. 26, 1909. Robert Wimmer, Germany. (Hoéchst.) 
Stable indigo-white and process of making same. _ Leuco indigo in stable water 
soluble form, for direct use in vat. 

Alkali salt of INDIGO WHITE, (made as in 820,900 from indigo in dil. NaOH reduced with Fe 
powder then filtered) is mixed with sulfite cellulose waste liquor (50 per cent solids) and evap- 
orated in vacuum or on water bath to dryness. 

Note 833,654 for related compound. 


999,055—July 25, 1911. Paul E. Operreit, Germany. (Badische.) 
Reducing indigo coloring-matters. Preparation of leuco indigo vat. 

Ferrous oxide, obtained by reducing ferric oxide with H at low temp., in dil. NaOH (at 
least 6.5 per cent) is warmed to 70° and INDIGO powder added. Metallic Fe can be used to- 
gether with ferrous oxide, and alk. carbonate instead of caustic alkali. Ferrous oxide which has 
become coated with a layer of ferric oxide by exposure to air may be previously treated with 


an acid. 
Note 820,900 and 843,566 for similar processes. 


1,005,481—Oct. 10, 1911. Albrecht Scumipt, Germany. (Hochst.) 
Preparation suitable for the indigo-vat. Leuco indigo preparation to reduce loss 
of indigo in dye vat. 

INDIGO WHITE, or its compounds with alkali or saccharine materials, as described in 906,307, 
is mixed with a salt of benzyl suLFANILIC acid, or other, (5-15 per cent on weight of indigo) 
or the salt is introduced during the mfr. of the leuco comp. Indigo formed during working of 
vat is so finely colloidal, that reduction is quick, and less indigo loss in sediment results. 


1,011,500—Dec. 12, 1911. Karl ScHNITZSPAHN, Germany. (Griesheim.) 
Process of making phenylglycin salts. Phenylglycin salt free from alkali chloride. 


To the PHENYLGLYCIN melt consisting of 1 mol. CHLORACETIC acid and 3 or more mols. ANILIN, 
is added one equivalent of a neutralizing agent such as alkali or alkali earth hydroxide, oxide or 
carbonate, sufficient to neutralize the HCl set free. Phenylglycin compounds separated from the 
resulting chloride are converted to alkali salts by NaOH. 

Note 818,341 (Gr. VII). 


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Ss Be eee 


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GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL, 42I 


1,026,754—May 14, 1912. Gadient Encr and Jaroslav FROHLICH, Switzerland. (Basle.) 
Process of dyeing and the product thereof. Application of dye 994,988 to cotton 
and wool. 


INDIGO, prepared as in 994,988 by condensing with spENzoyy chloride or other halide of aro- 
matic acids, and saponifying, is prepared for dyeing on cotton by mixing 1 part of dye with 3 
parts each of 36° NaOH and hydrosulfite powd. and for wool with half these quantities. After 
treatment on fiber with hypochlorite increases the purity of tint. Color is green yELLOw, fast to 
washing, light and chlorine. 


1,027,441—May 28, 1912. Albrecht Scumipt, Germany. (Hochst.) 
Isolated alkali salts of indoxyl and process of making same. Separating solid 
cryst. alkali salt of indoxyl, as crystals. 
InpoxyL melt is pulverized and mixed with equal weight ice, and the cooled and pptd. in- 


doxyl filt. through asbestos or sand, or centrifuged, pressed and freed from alkali by washing. 
Product forms cryst. plates of yellow tint, sol. in aq. and alc. (RBr). 


1,027,836—May 28, 1912. Wilhelm Gaus, Germany. (Badische.) 
Reducing indigo coloring-matters,. Preparing iron filings for indigo vat. 

Iron filings are pickled in acid to remove surface layer of oxide so that uniform results may 
be obtained by reduction of indigo in presence of caustic alk., which should contain at least 6.5 
per cent solid caustic. 

Note 820,900 and 843,566 for applications of above. 


1,029,066—June 11, 1912. Adolf Krerrrsz, Germany. (Cassella.) 
Process of dyeing vegetable fibers with halogenated indigo and indigoid 
dyestuffs. Dyeing halogen indigo and indigoid dyes in sulfide bath to reduce expense of 
process. 
Dye bath is charged with paste of halogen indigo or indigoid dye, with Na,S, NaOH and 
Glauber’s salt, and if desired with some hydrosulfite toward end of process. Other indigo de- 
rivs. can not be used in Na,S bath. 


1,043,016—Oct. 29, 1912. Adolf Kerrresz, Germany. (Cassella.) 
Dyeing of cotton or linen cloth with wvat-colors. Increasing penetration of vat dyes. 
Fabric, of heavy or tightly woven cotton or linen, is dyed with INDIGO or ALIZARIN derivs. 


in vat containing Na,S and NaOH for 1 hour at boil, then some hydrosulfite added and further 
heated at 65-70°. 


1,054,039—Feb. 25, 1913. Albrecht Scumipt and Adolf Srernporrr, Germany. (Hdéchst.) 
Stable indigo-white preparations and process of making same. Stable, non- 
fermentable conc. preparations of leuco indigo. 

InpIGO WHITE press cake is kneaded with 1-0.6 parts 50 per cent Lactic acid and conc. in 
vacuum to 30 per cent dye strength. lLactates or other substances containing lactic acid may be 
employed, such as alkaline agents and a sugar substance, at not too high temp. or concentration. 
Products are gray to brown bodies, sol. in dil. alk., pptd. by acids. 

Addition to 906,307. 


1,057,886—Apr 1, 1913. Albrecht Scumipt and Adolf Srernporrr, Germany. (Héchst.) 
Mode of manufacturing a new form of synthetic indigo. Indigo in finely di- 
vided condition. 


InpoxyL melt (20 per cent) or other leuco indigo or indol deriv., is diluted, and pptd. in 
presence of a small amount of RESORCIN, or other phenol, by oxidization with air. 


1,057,887—Apr. 1, 1913. Albrecht Scumipt and Adolf STrerinporr, Germany. (Hdéchst.) 


Process of manufacturing finely-divided colloid-like indigo. Preparing indigo 
in finely divided colloidal state. 


Inp1co powd. is added not too slowly to 7 parts sulfuric acid (60°) at low temp. until 
magma of colloidal indigo sulfate, noncryst., blue in thin layers, is formed and this is dissociated 
by water, best in the form of ice. Addition of suitable organic or inorganic substances aids for- 
mation of colloid. Product is filtered, washed, and triturated with caustic or other dividing 
agent. 

Note 671,344. 


422 DIGEST OF PATENTS 


1,058,019—Apr. 1, 1913. Albrecht Scumipt, Germany. (Héchst.) 


Synthetic indigo in a new form and process of making same. New physical, 
easily reducible form of indigo (colloidal). 


InpvIco salt, 4 parts in 40 parts 60° sulfuric, is mixed with 1 part benzyl suLFaninic acid, 
with or without starch, glycerin, kaolin, etc., to preserve colloidal form, pressed, washed, neut. 
All derivs. of indol that will directly produce indigo in presence of amino sulfonic acids con- 
taining the benzyl group are claimed. Products are easily reduced by alk. agents giving deep 
blue liquids which will not filter and contain no cryst. particles under the microscope. Inventor 
compares product with 671,344 and 820,869. See 1,058,020 and 1,005,481. 


1,058,020—Apr. 1, 1913. Albrecht Scumipt, Germany. (Héchst.) 


Synthetic indigo in a new form and process of making same. Colloidal in- 
digo, easily reduced in vat, and pigment therefrom. 


Inpico salt dissolved in 60° sulfuric containing NAPHTHOL sulfonic, or other, is diluted with 
or without starch, glycerin, kaolin, etc., to preserve colloidal form, pressed, washed, etc. Pig- 
ment is formed by pptg. soln. of paste containing added naphthol sulfonic, etc., with air, or 
other oxidizing agent. Lists of components and diluents are given. Claims are the same as in 
pat. 1,058,019 but instead of limiting to amino sulfonic derivs. of benzyl all aromatic acids are 
applied. 

Note 1,058,021 claims the dry product. See also 1,005,481 and 1,058,019. 


1,058,021—Apr. 1, 1913. Albrecht Scumipt, Germany. (Héchst.) 


Dry colloid-like indigo and process of making same. Dry colloid-like indigo 
easily reduced and with properties like natural indigo. 
Colloidal 1npIGo paste, 30 per cent, prepared as in 1,058,019 and 20, 1,057,886 and $%7, 
1,085,361 and 1,094,683 is dried in vacuum or in open air at usual temp., or at higher temp. in 
“Huillard app.”” or (b) ground with grape sugar, china clay, and a little NaOH, then dried. 


1,085,361—Jan. 27, 1914. Albrecht Scumipr and Adolf Strernporrr, Germany. (Héchst.) 


Mode of preparing finely-divided or colloid indigo dyestuffs. (Product also 
claimed.) Colloidal indigoes, easily reduced in vat. 


InpIGO paste (20 per cent), its analogs, substitution prods., etc., in aq., alk., or sulfuric 
soln. with 3-oxy BENZALDEHYDE, formaldehyde, or other aldehyde, is treated with air, or other 
oxidizing agent. The new physical form is characterized by being easily reduced, when made 
into paste yields a deep blue liquid that deposits with difficulty, gives a blue filtrate when filt., 
and under the microscope shows no cryst. particles. 

Addition to 1,058,019 and 1,058,020. 


1,094,683—Apr. 28, 1914. Albrecht Scumipt and Adolf Strinporrr, Germany. (Héchst.) 
Mode of preparing finely-divided or colloid indigo dyestuffs. Preparing finely- 
divided or colloidal indigo. 

AniIuLiIn sulfate or other primary, secondary or tertiary base, is dissolved in conc. sulf. acid 
(60°), INDIGO, indol, leuco indigo, or other indigo salt is added, and product poured into ice 
water containing a small amount of carbohydrate, aromatic base, or other. 

Note 1,058,019 and 1,058,020. 


1,096,060—May 12, 1914. Albrecht ScHmipt and Adolf Srreinporrr, Germany. (Hoéchst.) 
Preparation suitable for the indigo vat. Leuco indigo compound, readily reducible. 


Indigo paste, 20 per cent, or any indigo or indigo producing preparation, 100 parts, is mixed 
with from 4 to 20 parts benzyl suLFANILICc acid Ba salt, or of phenyl benzyl dimethyl ammonium 
chloride disulfo, or other aromatic acid, and ground or triturated for some time or heated and 
stirred at higher temps. Pastes may be dried with clay, starch, glycerine, or saccharine bodies, 
if desired. 

Note 906,306, 1,005,481, 1,058,019, and 20. 


1,106,970—Aug. 11, 1914. 
Karl Retnxine and Armand J. Srrecenmann, Germany. (Badische.) 
Compounds of leuco vat dyes with aralkyl compounds and process of mak- 
ing same. Stable aralkyl compound of leuco vat dye with or without metallic oxide. 
Dimethyl phenyl BENZYL ammonium chloride or other aralkyl compound, mixed in paste 
with reducing agent, such as glycerin, gum, formaldehyde sulfoxylate, etc., is printed on fiber 
dyed with indigo, steamed, thereby reduced, and combined so as to be stable with alk. and air, 


eH as om 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 423, 


and sol. in dil. alk. to produce white discharge. Yellow to red to brown comps., stable toward alk. 
or air; sol. dil. alk. (O), otherwise insol. Dye may be pptd. with zinc oxide or other pigment. 
Many processes for applying various forms of charge compound are described. 


1,133,031—Mar. 23, 10915. Rudolf Hutzier, Germany. (Badische.) 
Treating insoluble indigoid dyes. Producing indigoes in colloidal form, soluble in aq. 


Sodium INDIGO WHITE, Io per cent soln., is allowed to flow slowly at common temp. into 
sulfite cellulose waste while air is passed through so slowly that colloidal indigo, sol. in aq., is 
formed. Product can be filtered and indigo in filtrate after removing salts by dialysis and evap- 
orating, may be pptd. by acid without solubility being destroyed. Application to other indigoes 
is claimed. 


1,175,634—Mar. 14, 1916. Michael Inyinsky, Germany. (Wedekind.) 


Vat-dyestuff compounds suited for dyeing and printing. lLeuco indigo com- 
pound with magnesia, alumina, ZnO, etc., suited for dyeing and printing. 

Inpico, or deriv., is kneaded in ball with 1o per cent paste of Mg(OH), and hydrosulfite, 
with exclusion of air. Glycerin, glue, etc., may be added and dry comp. formed in vacuo. Or 
the reduced vat may be pptd. by Mg(OH), or MgSO,. Leuco comps. with Al, Zn, Fe, Sn, etc., 
can be made as above by double decomp. in dye vat in presence of alkali. 


1,188,543—June 27, 1916. Rudolf Hutzier, Germany. (Badische.) 


Treating insoluble indigoid dyes. Preparing indigo, thio indigo, etc., in colloidal form, 
soluble in aq. 


Benzyl antLin sulfo, or other salt of an aromatic sulfo acid, is dissolved in cold aq. soln. 
through which air is slowly passed while 1nDIGO WHITE, Na salt, is added, oxidation being car- 
ried out so as to avoid pptn. of color. Solution is filt., washed in osmctic apparatus and evap- 
orated to dryness, or colloidal dye may be pptd. by acid without losing its colloidal property. 

S. 874 or 912. 


1,239,526—Sept. 11, 1917. Albrecht ScHmipt, Germany. (Hdéchst.) 


Stable concentrated preparation for the indigo fermentation-vats. (Process 
claimed.) Stable conc. nonputrefiable comps. for indigo dye vat. 


Rye bran extracted by warm aq,, filt., evaporated in vacuo to syrup, and mixed with molasses, 
other saccharine substance, or glycerine. Other albuminous materials claimed. Conc. stable, 
nonputrefying indigo white products can be obtained by mixing leuco indigo with above paste. 
Readily sol. solid preparations result by evaporation in vacuum. 


1,247,927—Nov. 27, 1917. Andre Brocuet, France. 


Manufacture of leuco derivatives of vat dyestuffs. lLeuco indigo, derivs., or other 
leuco vat dyes. 


Synthetic indigo or derivs., indanthrenes, etc., 2 parts, mixed with 1 part reduced Ni or 
other hydrogenating catalyst in 100 parts of 1-2 per cent NaOH at 60-80°, are agitated wel! 
while H or gas containing H, such as water gas, is passed through till all is reduced. Nickel 
is allowed to settle and brownish yellow liquid of leuco dye drawn off. Heat and pressure accel- 
erate reaction. Alkali is not necessary but is preferable. 


1,341,637—June 1, 1920. John W. Fries, North Carolina. 
Method and product for dyeing textile fabric. Indigo vegetable dye comp. soluble 
in soln. of soap or soluble oil. 


Indigo, dry or as paste, is mixed with a vegetable dye extract, such as logwood, that has 
previously been reduced by fermentation with yeast or other catalyst. Ferment is used in dye 
vat by soln. in 1 per cent soap or soluble oil, or is marketed in dry conc. form for such use in 
dye vat. Color must be developed by after treatment with Fe, Cu, or Ni salt or equivalent. 


1,426,522—Aug. 22, 1922. 
Karl Tuikss, Fritz MAENNCHEN, Adolf STEINDORFF and Franz GiILroy, Germany. (Hidchst.) 
Stable, dry, and readily-soluble wat preparations and process of making 
same. Mixed leuco indigo and indigoid dyes in marketable form. 
Three parts leuco indigo and 1 part leuco quinone indigoid dye described in 1,128,368 
(sulfurized) or 1,009,981 (nonsulfurized) are mixed with nearly 4 parts 40° NaOH, 0.67 part of 
molasses or sulfite cellulose pitch, and 0.5 part hydrosulfite in 4 parts water to paste and evap. 


424 DIGEST OF PATENTS 


to dryness in vacuum to a solid porous form, which is vesicular, of dark color, very stable, and 
readily sol. in aq. to give BLACK wool dye. 


1,448,251—Mar. 13, 1923. Marcel Baper and Charles SunpgErR, France. (Durand.) 
Product for dyeing and printing textile materials and in general for pig- 

mentation of various substrata and proeess for the manufacture of the 

same. Alkylated leuco indigoes, stable in dry form, sol. in aq., and valuable for printing. 

Dry dehydro leuco 1npico powd., 1 mol., at o° together with CO, gas is added to the prod- 
uct of the action of chlor sulfonic acid, 2 mols. drop by drop, on about 8 mols. chlor BENZENE 
and 4 mols. dimethyl ANILIN at 0°, temp. is raised slowly to 60°, mass made alk. with NaOH 
(30 per cent) and distilled by steam, conc. in vacuum and dye salted out. Other dialkyl amins, 
other leuco indigoes and inert solvents such as pyridin may be employed. Buus reducing vat 
dyes. 


SUBGROUP IX.—NITRO. (Nt.) 


283,265—Aug. 14, 1883. Neil McCattum, Pennsylvania. (Leeds.) 
Composition to be used as a paint or dye. 

Picric acid and FLAVINE are mixed with 36° HNO, and boiled to dryness. Flavine is ni- 
trated and picric acid not affected, but process gives better dyestuff than simply mixing nitro 
flavine and picric acid mechanically. Product is green YELLOW to orange YELLOW acid dye, ac- 


cording to proportions of ingredients. 
“FEchurine.”’ 


412,680—Oct. 8, 18809. C. Savieny, France. (Martinon.) 
Process of treating the mothor-liquors of phenol nitrates. Recovering valuable 
constituents from mother liquors of nitro phenols. 

Mother liquors are heated to 48-52° to distil off a large part of HNO,, cooled to cryst. 
Picric and nitro cresylic acids, which when removed leave only a little picric and oxalic acids 
in sulf. acid. Acid is then diluted, to lower temp. to 15° and remove more picric acid. Residue 
is heated in open vessel to conc. to 65-66°, which removes residual impurities, leaving pure acid. 
Addition of HNO, during concn. will effect the nitration of unchanged phenols present. 

S. 5—‘‘Picric acid.” 


669,030—Feb. 26, 1901. Adam C. Girarp, France. 
Process of making picrates. Improved manufacture of picrates to avoid danger. 


Vegetable or animal oil, castor oil for instance, is used as solvent for picric acid, and the 
calculated amount of base in form of oxid or carbonate, pulverized to promote reaction, added 
thereto. Picrate is freed from oil by adding benzin, alc., ether or other suitable solvent. 


548,346—Oct. 22, 1895. Arthur AsHwortu and Joshua Burcrr, England. — 
Nitrosonaphthol dye and process of making same. VNitroso 2-naphthol bisulfite 
comp. 


Nitroso 2-NAPHTHOL, 1 part, is warmed to 25-30° with 2 parts sodium bisulfite (60 Tw.) 
or other bisulfite. The bisulfite comp. forms silver gray crysts., easily sol. aq. (colorless), de- 
comp. by NaOH, forming green ppt. of sod. salt; a GREEN (Fe) or Brown (Cr) acid mordant 
dye, valuable also for printing and as component of azo dyes. 

S. 4—‘“‘Naphthol Green B.” Note 548,416 (Azo) and 548,344 and 548,345 (Oxazin). 


615,232—Dec. 6, 1808. Hermann Att and Eduard Cunmann, Germany. (Kalle.) 
Process of dyeing with quinonoxim colors. Benzo and naphtho quinonoxim, etc. 


Fabric is impregnated with mitxure of a phenol, such as RESORCIN, 1-naphthol, dioxynaph- 
thalene, etc., a mordant such as copperas and a suitable acid such as tartaric acid, dried, then 
passed through a neut. boiling nitrite solution. Or a previously mordanted fabric is impreg- 
nated with mixture of a phenol and acid and passed through a nitrite soln. A GREEN mor- 
dant dye, useful for lakes in printing. 

S. 1 to 3—‘“‘Solid Green, Gambine Y. and B.” 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAI, 425: 


1,031,823—July 9, 1912. Otto Stacuiin and Karl ZecuentMAyvER, Germany. (Hochst.) 
Color-lakes and process of making same. (Process not claimed.) Ferro bis-(1-ni- 
troso 2-naphthol 5-sulfo) or the 3-sulfo deriv., in form of lakes with alum, baryta, etc. 


I,2-NAPHTHALENE DIAMIN 3- or 5-sulfo, ferric comp., is pptd. in alk. carbonate soln. by alu- 
minum sulfate and barium salts. A blue GREEN to gray BLUE lake, fast to water, acids, alk., 
lime, oil, and especially to light, and adapted for printing. 

Near S. 4—‘‘Naphthol Green B.”’ 


SUBGROUP XI.—OXAZIN. (Ox.) 


255,349—Mar. 21, 1882. James H. Sressins, Jr., New York. 


Dyeing blue colors upon textile fabrics. (Product, not process, claimed.) Processes 
for developed dyeings on wool, cotton-wool mixture, etc., improved by treatment with bi- 
chromate. 


(@) 1I-NAPHTHOL is applied to cotton or calico in alk. soln., dried, printed with nitroso 
diethyl ANILIN and glucose and steamed to develop color. (b) Or cloth is impregnated with alk. 
glucose, dried, printed with mixture of two dye components and developed. (c) Or nitroso 
comp. reduced with Zn, is filtered, 1-naphthol and starch paste added, printed, and steamed. 
Prepared cloth is then passed through hot soln. of bichromate to develop color more fully. 

Isomer S. 649—‘‘Meldolas Blue.” Note 252,273, among dyes for sulfonated Meldola’s Blue. 


257,498—May 9g, 1882. Horace Korcuiin, Germany. 


Manufacture of coloring-matter. Leuco form of 253,721, dimethyl 3-amino 5.6-di- 
hydroxy phenoxazin 8-carbo acid. 


Dye is reduced in neutral or alk. soln. by Zn dust. 
S. 626—“Gallocyanin.”’ Note 962,712 for leuco form by reduction in acid soln. with Zn. 


629,666—July 25, 1899. Charles p—k LA Harpr and Charles Vaucuer, Switzerland. (Durand.) 


Gallocyanin-leuco derivative and process of making same. Leuco form of 
gallocyanin dyes for printing and dyeing. 
Dye is reduced with Zn and HCl, or other agent. 
S. 635—“Blue 1900 T. C. powd.’”’ Note 863,907 for closely similar specifications. 


649,228—May 8, 1900. Eduard Uuiricu, Germany. (Hochst.) 


Process of fixing quinonimid dyes. Developing and fixing on fiber the chromium 
compounds. of quinonimid dyestuffs from their components. 


Nitroso dimethyl anizin HCl in aq. soln. with starch thickening and GLYCERIN is com- 
bined with soln. of Persian berry extract and an organic acid, tartaric or oxalic, etc., and of 
chromium acetate, then printed on fiber, steamed, etc. Other dye components claimed. 


649,227—May 8, 1900. Eduard Uniricu, Germany. (Hochst.) 


Process of dyeing quinonimid dyes. Quinonimid dyes as developed colors. 

N-Alkylated oxazin, oxazone or azin dyes derived from nitroso comps. of secondary and 
tertiary aromatic bases combined with amins, diamins, phenols, etc., are dyed or printed as 
basic mordant colors and developed on fiber. Nitroso dimethyl anin1In in dil. starch paste soln. 
containing acetate and glycerin, added to soln. of 2.7-dioxy NAPHTHALENE in dil. acetic, and soln. 
of oxalic acid, then TANNIN soln. added. Product is printed or padded on fiber, dried at 50°, 
steamed, and developed in antimony bath. If necessary, dyeings are treated with Cl. Modified 
- methods and other components described. 


663,220—Dec. 4, 1900. Charles pk tA Harps, Switzerland. (Durand.) 


Gallocyanin-sulfonie acid and process of making same. Process for oxidation 
of leuco gallocyanin sulfo acids. 
Leuco GALLOCYANIN sulfo acids derived as in 663,221 are dissolved int dil. NaOH and soln. 
agitated in air, neutralized by acid, and pptd. by salt, etc. 


704,201—July 8, 1902. | Charles p—E LA Harps, Switzerland. (Durand.) 


Leucogallocyanin and process of making same. Leuco form of ethyl benzyl gallo- 
cyanin sulfo. 
Patent is similar to 629,666 except that a sulfonated gallocyanin is reduced using Zn and 
acetic. 
Near S. 635—‘“‘Blue 1900 TC. Powd.” 


426 DIGEST OF PATENTS 


807,182—Dec. 12, 1905. 
Charles Oswatp, Hermann Loreran and Charles p—E LA Harpe, Switzerland. (Durand.) 
Green dye and process of making same. Leuco deriv. 

Nitroso diethyl ANILIN condensed with GALLAMIc acid, is treated with FORMALDEHYDE and then 
with bisulfite, Zn and HCl, formaldehyde bisulfite, or other, in acid soln. GREEN acid mordant 
(Cr) dye, suitable for printing. 

S. 629—“‘Gallo Green D H.” 


844,155—Feb. 12, 1907. Herman Loreran, Switzerland. (Durand.) 
Leueco derivatives of gallocyanins and aromatie amins and process of mak- 
ing same. Leuco form of dimethyl gallocyanin amid, in which H and OH are substi- 
tuted by diamins, 
Dye of 844,156 is reduced by three methods (a) with Zn and HCl, (b) by Na,S and (c) 
by electrolysis with carbon anode and Pb or Pt cathode. 
S. 627—‘‘Modern Cyanin.” 


1,227,407—May 22, 1917. 
Gadient Enc1, Armin Gros and Jakob Wurc ier, Switzerland. (Basle.) 
Chromium compounds of the gallocyanin series and a process of making 
same. Soluble chromium compound of pyrogallol gallocyanin. 


GALLOCYANIN, derived from nitroso dimethyl ANILIN and GALLIC acid, is heated in soln. of 
sodium acetate and bichromate or CrF,, etc. Process for printing described. 


SUBGROUP XIII.—QUINOLIN. (Qua.) 


1,803,426—May 13, 1919. Edward J. Watt, New York. (Kalmus.) 
Dye recovery. Recovering dye from color sensitizing collodion or gelatin emulsions. 

A metallic salt (Al, Sn, Fe, Cr, etc.) and an alkali are added to the dye solution and re- 
sulting colloidal hydroxide thoroughly agitated until dye is absorbed. An inert substance such 
as BaSO, may be pptd. in soln. and in this case dye is probably adsorbed. Separated ppt. is dried 
and dye extracted by alcohol or other solvent. Tannin is not suitable as pptg. agent. 


1,337,673—Apr. 20, 1920. Edward J. Watt, New York. (Kalmus.) 
Dye recovery. Recovery of photosensitive dyes from bath, after use. 

Photosensitizing dyes of the isocyanin type, which are basic, are recovered from soln. by 
introducing cellulose material, or other insol. dye-absorbent matter in fibrous or finely divided 
form, impregnated with a dye mordant such as hydroxide of Al, Sb, Fe, Sn, etc. and a binding 
agent like tannin. The dye is then extracted from the absorbent material with alcohol or 
other suitable solvent. 


SUBGROUP XV.—SULFUR. (Su.) 


549,036—Oct. 20, 1805. Raymond VipaL, France. (St. Denis.) 


Process of treating sulfur compounds of aromatic series with sulfites. (Prod- 
uct claimed.) Soluble bisulfite compounds of sulfur colors. 


Sulfur dyes, obtained by heating at 180° 4-amino PHENOL or other bi-substituted aromatic 
compounds with sulfur and NaOH, is mixed in form of 15 per cent paste with cryst. sulfite of 
Na, and used directly or dried and powd. Powds. are insol. in usual solvents but sol. in alks. 
and alk. sulfids. 

Near S. 717—“‘Vidal Black S.” Addition to 532,484. Note 549,032 for a special dye from 
Cachou de Laval. 


549,082—Oct. 29, 1895. Raymond Vipat, France. (St. Denis.) 

Process of treating cachou de laval. Soluble compound of Cachou de Laval. 
CACHOU DE LAVAL is dissolved in hot aq., pptd. by acid, washed with dil. HCl, resulting dye 

paste mixed with cryst, soda sulfite or bisulfite, let stand 3 days, filt. and used direct or dried to 


powder. 
S. 706—‘“‘Cachou de Laval.” Addition to 549,036. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL, 427 


625,717—May 23, 18909. Martin BorHLEer, Germany. (Cassella.) 
Process of dyeing dark blue. 


Cotton dyed with IMMEDIAL BLACK V, extra (derived from oxy dinitro DIPHENYLAMIN), is 
warmed in bath containing 10 per cent H,O, for 30 min. at 80°. Dark sLuE developed (oxidized) 
sulfide vat dye. 

S. 724—“Immedial Blue C.” Addition to 610,541. 


646,760—Apr. 3, 1900. Alcide F. Porrrier, France. 


Process of mordanting. Fixing sulfur color with copper and chromate salts so as to pre- 
vent tendering of cotton, spotting and rubbing. 


Fabric dyed with sulfur color is passed through bath of 2-3 per cent chloride of copper or 
any cupric combination other than sulfate (to avoid action of free sulf. acid on cotton cloth), 
also a salt of copper may be used in part for bichromate. To further improve the process the 
dye should be freed from sulfids, sulfites, polysulfide, etc., before use and goods should be com- 
pletely immersed in bath throughout process of dyeing. 


647,493—Apr. 17, 1900. Ewald Hé.ixen, Germany. 


Process of mordanting. Treating black sulfur dyeings, so that cotton color will not bleed 
into white wool. 


Black cotton yarns are warmed at 40-50° in bath containing 4-6 per cent zinc sulfate, 2-3 per 
cent bichromate, and 2-3 per cent sulf. or other acid, boiled, and excess zinc salt washed out. 
The zinc chromate fixes the color firmly, the bath remaining clear and colorless. Zinc salt 
should be in excess for best results. 


660,069—Oct. 16, 1900. Friedrich BrREUNINGER, Germany. (Cassella.) 


Process of dyeing sulfur colors. After treatment of sulfur dyeings to develop color 
and prevent tendering. 


Dyed fiber is treated with chromous instead of chromic salts, which cause tendering. Chrome 


alum, 3-5 per cent, so used with IMMEDIAL BLACK will give fuller and deeper shade. For dyes 
requiring oxidation chromate is used in less amounts, together with chromous salts. 


665,737—Jan. 8, 1001. Emil HaussMANN, Germany. (Berlin.) 
Process of dyeing. Dyeing in sulfide vat in presence of organic matter and caustic. 

Dye such as IMMEDIAL BLACK or other sulfur dye, is ground with equal part NaOH and of 
boiling aq., then 1 part glucose added and mixture heated until a clear liquid forms. Instead 
of glucose, other organic materials, such as lactic acid, dextrine, milk sugar, etc., which with 
NaOH act as reducing agents, are claimed. Products may be used for printing and will not 
corrode metallic parts. 


678,884—July 23, 1901. Adolf Kerrrsz, Germany. (Cassella.) 
Process of producing blue sulfur dye. Black sulfur dyes oxidized on fiber to blue. 


Fibers dyed with sulfur dyes, such as IMMEDIAL BLACK, Vidal Black, Kryogen Blue, or other, 
in Na,S vat are treated without washing or drying, with air, or oxygen and steam under high 
tension (over 100°). ‘The fiber should show alk. reaction, ammonia being added if necessary. 


680,472—Aug. 13, 1901. Max Becxe and Albert Brit, Germany. (Hodchst.) 


Process of dyeing with sulfur dyes. Dyeing sulfur dyes from completely reduced 
hydrosulfite vat. 

Sulfur dyes such as IMMEDIAL BLUE C, Immedial Black G, Katigen Blue, Noir. Vidal, etc., 
are best pptd. as dye acids by oxidizing or acidifying the soln. of the raw Na,S melt, then are 
reduced to leuco form and dyed in a hydrosulfite vat the same as with indigo, lime not being 
required, then oxidized on fiber, and fixed by metallic salts. Several dips may be made, and 
fixation with metallic salt after first dip has unusual effect in increasing strength of color. Indigo 
and sulfur dyeings may be made jointly. 


681,117—Aug. 20, 1901. Arthur G. Green and A. MEyYENBERG, England. (Clayton.) 


Process of dyeing thiosulfate colors. Dyeing sulfur colors in leuco form in glucose- 
alkali vat containing sulfites. 

CLAYTON FAST BLACK or other sulfur color in form of free dye acid (separated from Na,S 
soln. by air or CO,) is dissolved in neut. sod. sulfite to form sol. sulfite comp. and bath reduced 
by repeated additions of glucose and alk., or other reducing agent, in presence of fiber which 

28 


428 DIGEST OF PATENTS 


takes up the leuco dye evenly. Dyeing is washed, and to produce high degree of fastness is 
oxidized in a hot soln. of 3 per cent CuSO, and 1 per cent Na,Cr,O, in 3 per cent acetic acid. 


693,653—Feb. 18, 1902. A. Kartesz. (Cassella.) 


Process of dyeing sulfur colors. Process for after treatment of sulfur dyeings with 
acetates or similar salts to prevent tendering. 


Velvet dyed with IMMEDIAL BLACK, or other sulfur color in Na,S and salt soln., is rinsed, 
treated with bichromate, chrome alum, and acetic acid and after rinsing, again passed through 
acetate of soda soln. and dried without rinsing. 


708,429—Sept. 2, 1902. Ernst Vorrrer, Germany. 


Process of printing with sulfur dyes. Printing compound of sulfur dyes that will 
not attack copper rollers. 

Sulfur dye is rubbed up with finely divided sulfur and an equal quantity of aq., thicken- 
ing agent added, cooled, and finally alkali carbonate soln. stirred in immediately before printing. 
Goods are printed, dried, steamed 0.5 hour at 3.75 lbs. pressure, washed well and treated boil- 
ing in soap bath. Copper or chromium salts, sulfites or hyposulfites may be added to the paste, 
other proportions of ingredients may be used and any sulfur dye. 


714,687—Dec. 2, 1902. Emil A. Fournraux, New York. (Metz.) 
Process of making lakes from sulfur dyes. [Lakes of sulfur dyes. 


Any sulfur dye, comm’! form, such as MELANOGEN BLUE, in aq. soln. is pptd. by alkali earth 
salt, filt., ppt. thoroughly washed, suspended in alk. carbonate soln. and boiled with salts (pref- 
erably sulfates) of Al, Cr, Ni, Co, Zn, Cu, Pb, or alk. chromates, bichromates, etc., keeping 
alkaline. Combination lakes with acid, basic, or alizarin colors may be made,—see examples. 


717,7%749—Jan. 6, 1903. Oscar JaEcK, Germany. (Elberfeld.) 


Process of dyeing. Sulfur dyeings after treated with neutral sulfite to produce brighter 
and faster shades. 

Fiber dyed with 10 per cent sulfur dye such as IMMEDIAL BLUE CR, is rinsed, exposed to air, 
then (a) placed in bath of 0.2 per cent neut. sod. sulfite at 80° for 30 min., rinsed and dried, 
or (b) passed 2-3 times through bath of 0.5 per cent Na,SO,, squeezed and dried without rins- 
ing. Conditions may be varied within wide limits. Higher temps. and larger proportion of sul- 
fites shorten time of treatment. 

Note 688,999. 


724,681—Apr. 7, 1903. Ernst Vorrrer, Germany. 


Process of dyeing with sulfur dyes. Sulfur dyeings on jigger without discolored edges, 
and apparatus therefor. 

In dyeing sulfur dyes on jigger, to avoid discolored edges due to drying and to oxidation 
by air at high temp., cold water is poured continuously on the edges of the unwinding roll of 
goods to keep edges wet and lower temp. Cold diluted dye liquor with added Na,S or fresh 
Na,S dyestuff soln. may be applied. Drawings and description of apparatus are given. 


747,295—Dec. 15, 1903. Edmond Bourcart, Germany. (Thann.) 
Process of printing sulfur dyestuffs. Stable printing compound of sulfur colors that 
does not attack copper rollers. 

A commercial sulfur color that has been pptd. from soln. by acids and washed free of acid 
(still containing free sulfur) is mixed to paste with thickening, with a neutral or acid carbonate, 
and a reducing agent such as thiosulfate, sulfite, formate, xanthate, sulfur, glucose, etc. The 
sulfur and other reducing agents act only when printed cloth is steamed. 


764,735—July 12, 1904. Richard Laucu, Germany. 


Process of making sulfur dyes stable. Reduced sulfur dyes in fine powd. oxidized to 
prevent spontaneous combustion or deterioration in commercial packages. 


Dye prepared as in 764,733 and 764,734 is oxidized in air by stirring or turning over for 
3 days or more, before packing for storage or market. 
S. 727—‘“‘Auronal Black.” 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 429 


769,059—Aug. 30 1904. Henry J. Cooxse, New York. (Klipstein.) 
Oxidizing sulfur dye. Oxidizing sulfur dyes by ozone. 


Fiber dyed with sulfur dye or other oxidizable dye, without rinsing, is treated in air cham- 
ber at 60° with current of ozonized air, oxygen, or steam charged with vapor of essential oil, 
especially TURPENTINE, by previous passage through an adjacent chamber of absorbent material 
containing the essential oil. Vapors condense on fibers and dye is oxidized at low temp. 


772,931—Oct. 25, 1904. Richard Guiry, Germany. (Berlin.) 
Process of making lakes from sulfur dyes. Lakes from sulfur dyes. 


IMMEDIAL SKY BLUE, is dissolved in dil. Na,S to which Na,CO, and BaCl, are added and air 
bubbled through till oxidation is complete. Other sulfur dyes that form pale colored leuco comp., 
other metallic bases and oxidizing agents claimed. 

Addition to 714,687. 


873,277—Dec. 10, 1907. G. A. Watpincer and C. F. Isernotu, Germany. (Bayer.) 
Process of dyeing. Dyeing sulfur dyes in presence of neutralizing agent for free alkali. 


To a dye bath of sulfur dye, such as KatTIGEN INDIGO RI, extra, containing Na,S and glau- 
ber’s salt, is added NaHCO,, or the bisulfate or bisulfites of Na, of Al, acetate of Al, cream of 
tartar, or other salt of fixed base capable of binding alkali, in sufficient quantity to neut. alkali 
but not ppt. dye. 

Note 873,613, 873,636, and 882,543. 


873,613—Dec. 10, 1907. Georg Rupotpn, Germany. (Bayer.) 
Production of effects on mixed goods composed of cotton and wool. Dyeing 
sulfur dyes on mixed cotton and wool goods. 


To produce varicolored effects with sulfur dyes on mixed wool and cotton goods, the wool 
is protected by chroming the wool yarn before weaving with the cotton. The cotton of the 
mixed cotton and chromed wool cloth is then dyed in usual sulfur bath in presence of organic acids 
having a reducing action, such as formic, lactic, etc., to protect chromium comps. on wool. 
Wool can be dyed before weaving with cotton, or after sulfur dyeing, or may be left white. 

Note 873,277, 873,636, and 882,543. 


873,636—Dec. 10, 1907. Hans Torrrer, Germany. (Bayer.) 


Process of dyeing. Dyeing sulfur dyes even shades in presence of alkali neutralizing agent. 
Sulfur dye bath is prepared in usual way and to it is added (NH,),CO, or other ammonium 
salt, with or without soft soap. Level and uniform shades are produced in many cases, deeper 
and faster to washing than when NH, salt is not used. Moderate temps. of bath are better on 
account of NH, sulfide evolved. 
Note 873,277, 873,636, and 882,543. 


882,543—Mar. 17, 1908. Gustav A. WatpINGER and Carl F. Istrnotu, Germany. (Bayer.) 


Process of dyeing. Sulfur dyeing in presence of alkali neutralizing agent. 
Sulfur dye bath is prepared as usual with addition of sulfuric, acetic, or other acid, in 
sufficient amount to neut. alkali set free during dyeing, avoiding an excess which would ppt. dye. 
Note 873,277, etc. 


895,689—Aug. 11, 1908. William Scuitenck, Germany. (Weiler.) 
Process of making indophenol-like condensation products. Improved method 

of making indophenol-like comps. for sulfur dyes. 

1-NAPHTHYLAMIN or other aromatic amin or deriv., is mixed with 4 parts NaCl or other 
indifferent diluent, and to this is added 1 part QuiNoneE chlorimid, keeping temp. below 30° to 
form an indophenol like condensation product. The amin is used in the form of its salt, or 
acids or acid salts, mineral or organic, may be used as condensing agents. Products are ob- 
tained as stable, dry solids, in almost quantitative yields. 


901,705—Oct. 20, 1908. Max Griwnpaum, Switzerland. (Basle.) 
Printing sulfurized dyestuffs. Sulfur dye printing pastes that will not attack brass 
rollers. 


Printing pastes from sulfur dyes are made by adding to paste conc. Na,S, with or without 
strong caustic alk., of sufficient strength that brass rollers are not attacked and blackened. When 
polysulfids are present hot printing paste is mixed with hydrosulfite to destroy them. 


430 DIGEST OF PATENTS 


901,746—Oct. 20, 1908. Albrecht Scumipt and Otto Scnwas, Germany. (Hoéchst.) 
Process of making concentrated liquid dyestuffs. Conc., completely dissolved, 
sulfur dyes. 
Trinitro amino DIPHENYLAMIN from 2.4-dinitro chlor BENZENE and nitro 3-PHENYLENE DIAMIN 
is converted by polysulfides into sulfur dyestuff, Na,S then added while moist to attain a cer- 


tain fluidity measured by viscosimeter and varying with dye under treatment. Other sulfur dyes 
similarly treated. 


907,937—Dec. 29, 1908. A. WEScHER, Germany. (Héchst.) 
Process of dyeing sulphur dyes. Dyeing with sulfur dyes, on wool, silk, half wool, half 
silk, leather, furs, paper, etc. 
Dye bath is prepared is usual manner with sulfur dye, Na,S and salt to which a large 
quantity of bisulfite is added to neutralize injurious effect of alkali sulfid on fiber so that wool 
can be dyed at high temp. of 70-80°. Sufficient bisulfite must be present to render bath neutral 
to phenolphthalein. Deep shades obtained by 1-3 minutes immersion, etc. 


953,008—Mar. 22, 1910. Emil HaussMANN, Germany. (Berlin.) 
Compound of sulfur dyes soluble in water. Sulfur dye sulfite compounds, 


SULFUR BLUE L, extra, or other sulfur color in alk. sulfite soln., is oxidized by air or other 
oxidizing agent. Products are pptd. by metallic salts (Ba, Cu, Pb, Al., etc.) from aq. soln. to 
form deep colored lakes, and are dark to black powds., sol. in aq., give off SO, with acids, and 
are suitable for lakes or for dyeing chromed leather. 


960,975—June 7, 1910. Ludwig Licrenstrin, Austria-Hungary. 
Process of fixing sulfid colors. Producing well-fixed sulfide color prints. 


Fiber is impregnated with hot soln. of glue or other animal colloid, and printed with mix- 
ture of sulfide color, reducing agent and FORMALDEHYDE. For printing alongside of ice colors 
glue soln. is mixed with 2-NAPHTHOL or other coupling agent and castor oil soap. Claims of re- 
lated patent are discussed. 


1,095,237—May 5, 1914. A. Scumipt and A. StreinporFF, Germany. (Hochst.) 
Leueo-alkali preparations of sulfur dyestuffs and process of making same. 
Stable leuco-alkali preparations of sulfur dyes, soluble in water and ready for vat. - 


Sulfur dye is boiled in 40° NaOH soln. of glucose or other carbohydrate, and evaporated to 
dryness in vacuum with or without a little hydrosulfite. 


1,141,148—June 1, 1915. A. Scumipt and A. STEINpoRFF, Germany. (Hochst.) 


Leuco compounds and process of making same. Stable conc. leuco comp. of Hydron ~ 
Blue series, that may be used directly in vat. 


4-Nitroso PHENOL is condensed with N-methyl CARBAZOLE, or other N-alkyl Prey to form 
N-methyl carbazole INDOPHENOL, a dye of “Hydron Blue” series, the leuco form of which is 
mixed as conc. press cakes with molasses, glucose, glycerin, or other non-drying soluble body. 
Alkali salts of leuco dye also used. 


1,200,055—Oct. 3, 1916. Ernst VorrrEer, Germany. 3 
Process of making sulfur dyes. Sulfur dyes chemically combined with Na,S. 


Sulfur dyes such as those described in 655,659, or other diphenylmin, indophenol, or 3- 
diamin sulfur dyes, that have been pptd. from melt, are mixed with alk. sulfide in such amounts 
that all will combine chemically. Illustration gives 100 parts dye to 30-35 parts Na,S. Products — 
in aq., or alk. soln. at usual temp., used as printing comps., leave metal rollers unblackened, and a 
are decomp. with acids or steam. 


1,383,071—June 28, 1921. A. C. Burrace, Jr., and G. Meiset, Massachusetts. (Atlantic.) e 


Method of preparing sulfur-black and the product thereof. Preparing sulfur 
black in soluble, not readily oxidizable form. r 


SULFUR BLACK, pptd. by aeration from the diluted melt, is allowed to sediment upon a 
filter bed, water decanted, residue filtered by suction, and suction continued after it “breaks,” — 
air being drawn through layer of dye until it forms a moist friable powder. Drawings of — 
suitable sedimentation suction tank are given. y 

Note 1,383,072 for product claims. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 431 


1,383,072—June 28, 1921. A. C. Burrace and G. Metsert, Massachusetts. (Atlantic.) 
Sulfur-black. 
SULFUR BLACK containing water in association with solid color in quantity which guards 


against deterioration by oxidation, yet renders it readily soluble and miscible with salt or other 
diluent is claimed as product of process given in 1,383,071. 


SUBGROUP XVIII.—TRIPHENYLMETHANE, ETC. (Tr.) 


34,840—Apr. 1, 1862. Nathaniel Lioyp and John G. Date, England. 
Improvement in dyeing and printing with aniline colors. Applying basic anilin 
colors on tannin and antimony tartrate mordant. 

For printing, dye mixture contains gum water, tannin 3-20 oz. per gal. and color such as 
mative or magenta. These are printed on “unprepared” cloth, aged over night, steamed and 
passed through soln. of antimony tartrate at boiling temp. For dyeing, tannin is first applied 
to the goods, which are aged, steamed, passed through bath of antimony tartrate then dyed in 
acid soln. of color. More tannin gives darker shade. 


49,958—Sept. 12, 1865. August S. L. Leonnarpt, Germany. 
Improved method of preparing aniline colors for dyeing and printing. 
Purification of commercial blue and violet MAGENTA and precipitation in finely divided state 
suitable for application in dyeing and printing. 
Water insoluble ROSANILIN dye, dissolved in hot alcohol, anilin or conc. sulfuric acid, etc., 
is added in fine stream to large volume cold aq., or salt, caustic, carbonate or other soln. 
while stirring vigorously. 


51,404—Dec. 5, 186s. John Hotuimay, England. 
Improvement in the manufacture of coloring-matter. Method for purification. 


Cotton violet dyes or ROSANILIN residues are pptd. with dil. alk. or salts and ‘further purified 
by dissolving in acid alc. and pptg. by alk. 


76,031—Mar. 24, 1868. Emil ZinssMANN and Charles Rumprr, New York. 
Improved compound of aniline colors. Rendering dyes soluble so that expensive al- 
cohol is not required. 

Alcohol soluble anilin dye, such as “‘Parme”’ or ANILINE BLUE, etc., is added to mixture of 
glue and acetic acid, thoroughly ground and mixed then heated on water bath. For purple dyes 
it is preferable to use gums or dextrin and replace acetic acid by glycerin or decoctions of 
plants such as soap wort. 


171,787—Dec. 8, 1875. Otto FrioritiLo, Maryland. 
Improvement in processes of manufacturing aniline bronze. 

ANILIN RED (Fuchsin), 2 parts, mixed with 1 part ANILIN PURPLE (Hoffman’s Violet) is dis- 
solved in 20 parts 95 per cent alc. by heating on sand bath then 1 part BENZoIc acid and about 6 
parts gum benzoin added and boiling continued until green color becomes golden bronze. Color 
has many uses as pigment dye for paper, wood, glass, tin, china, leather (shoe polish) and for 
metals. 


297,844—Apr. 29, 1884. 
A. I. Francois Porrrifr and Daniel A. RosenstigHL, France. (St. Denis.) 
Sulpho-conjugated violets of Paris. In sulfonating Paris vio.et, free acid of sul- 
fonating bath is neutralized by base that forms a soluble salt. 

Paris Violet sulfo deriv. is formed as usual and after dilution the sulfonating acid is neu- 
tralized by carbonate of K, Na, NH,, Zn, Mg, or other salt of base that forms a soluble sul- 
fate, instead of lime usually employed. 

S. 516—‘‘Methyl Violet.” 


385,426—July 3, 1888. John C. Penninctron, New Jersey. 
Dyeing. “Dry dyeing’? with basic anilin dyes. 

ANILIN BLUE or other basic color, separated as free color base, 1s applied in ether soln. to 
the fabric, steamed to volatilize and recover ether, and sufficient acetic or other volatile acid 
added to form salt with color base in the material. Method may be varied. 


432 DIGEST OF PATENTS 


888,942—May 26, 1908. : _ Joseph Turner, England. 


Direct cotton dye. To produce direct cotton dyes faster to light and alkalies, and more 
brilliant than originals. 
Sulfonated tri beta naphthylated RoSANILIN with or without CHLORAZOL BLUE, or other direct 
cotton dyestuffs, is heated with oxaLic or tartaric acids, acid sodium sulfate or other easily dis- 
sociated salt. Numerous combinations claimed. 


1,043,271—Nov. 5, 1912. 5 August Stock, Germany. (Hochst.) 


Yellowish-green pigment dyes and process of making same. Yellow green dye 

lakes fast to light, lime and water. 

Tetra alkyl diamino 4-chlor TRIPHENYLMETHANE dyes are pptd. on a suspension of green earth, 
(natural Mg-Fe-Al-Ca silicate) or by tannin, soaps, rosin, potassium silicate, etc. 

Note 1,085,178. Dye from para chlor benzaldehyde gives a yellow-green color having many 
advantages over a mixture of a blue-green non halogenated triphenylmethane dye with Auramin. 


1,085,178—Jan. 27, 1914. Albert StrupLer, Germany. (Hoéchst.) 


Color-lake and process of making same. Yellowish green lakes fast to light, lime 

and aq., from tetramethyl 4.4’-diamino 3”-nitro 4”-chlor triphenyl carbinol. 

3-Nitro 4-chlor MALACHITE GREEN or 3-nitro 4-chlor Brilliant Green in soln. is caused to act 
upon green earth, in suspension, or upon tannin, soaps, solution of rosin, potassium silicate, 
etc. Color of lake is yellower than preceding patent. 

Addition to 1,043,271. 


1,209,423—Dec. 109, 1916. Arthur W. Fisuer, New York. 
Dyad dye. Prepared dye mixture. 


MALACHITE GREEN, 17 parts, in aq. soln. mixed with soln. of 1 part CRYSTAL VIOLET, used as 
stock soln. or evaporated to dryness for market. May be topped with any dye to vary shade. 


1,355,048—Oct. 5, 1920. John L. Kanes, Pennsylvania. 


Process of producing dyes of the magenta type. Improved commercial form for 
triarylamin dyes. 

In the production of MAGENTA or other triarylamin dye from 1 part ANILIN and 4 parts 
mixed TOLUIDIN, after the usual condensation about 1.5 parts dry starch paste and nearly 5 parts 
conc. HCI (1.2) are added, temp. raised to 130°, additional 0.5 parts anilin, 2 parts com’l. 
toluidin, 4 parts nitrobenzene, and a small amount metallic Fe in HCl are added and the whole 
refluxed at 180° for 6-8 hours. 


1,357,482—Nov. 2, 1920. ' Aba v. Sztanxay, Hungary. (Chem. Found.) 


Process for preparing combinations of phenolphthalein with carbonates 
of alkali metal. Alkali carbonate double salts with phenolphthalein for medicinal use. 
Conc. aq. soln. of carbonates of alkali metals are used for preparing alkali salts of PHENOL- 

PHTHALEIN, for immediate use. For instance, 0.4 gr. phenolphthalein dissolved in 15 ccm. abs. 

alc. is diluted with 800 ccm. distilled aq. ‘The fine emulsion formed is dissolved when 0.4 gr. 

anhyd. Na,CO, in 135 gr. distilled aq. is added without heating. The violet liquid contains 
sesquisodium carbonate of phenolphthalein. Other alkalies may be used. 


SUBGROUP XIX.—XANTHONE. (Xa.) 


192,201—June 19, 1877. Re. 9,939—Nov. 22, 1881. Isabella J. van SKELLINE, New York. 
Improvement in processes of dyeing tissue and bonbon papers. Dyeing papers, 
pink to red. 

Eos1n, aurin or fluorescein deriv., is dissolved in aq. or in sat. aq. soln. of stannate or 
bromide of Na, or acetate of Pb, Zn or Sn. Edges of paper are dipped in dye soln., dried, etc. 
Color may be fixed by bath of alum. 

Note 187,405 for related product. 


643,265—Feb. 13, 19009. Charles E. GassMANN, Germany. (Soc. Chim.) 
Solution of phthalein in phenol. Printing and dyeing fabrics with phthalein dyes. 


Dialkyl RHODAMIN or other phthalein, is dissolved by warming in phenol containing acetic 
acid, then tannin in acetic soln. and thickener added, and fabric printed or dyed, steamed, fixed 
by tartar emetic, washed, soaped, etc. 


4 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 433 


APPLICATIONS IN GENERAL, INCLUDING CELLULOSE DERIVATIVES. 


41,066—Jan. 5, 1864. Robert H. Grarrix, England. 


Improvement in dyeing and printing with anilin colors. Applying basic dyes 
on fiber, and for printing. 

A comp. of tannin with the anilin colors (basic) is formed during the process of dyeing or 
printing, cloth being prepared with salts of Sn or other suitable mordant. For printing, dye is 
pptd. from aq. soln. by extract of galls, redissolved in acetic acid or alc., etc., thickened with 
gum and is ready to print or dye on prepared cloth. 


46,200—Jan. 31, 1865. Thomas Crossty, Connecticut. (Amer. Cloth.) 


Improvement in the dyeing, printing, and manufacture of waterproof 
flocked cloth. Dyeing cloth coated with rubber, gutta percha or gum. 

Cloth is steamed at 105—143° for 20-30 m. to develop all chemical action, then passed through 
bath of SnCl,, followed by a bath of aq. NH, and Na,CO, to neut. acids, next an oxidizing bath 
of dil. H,SO, and Ca(OCl), and finally passed through dil. H,SO, to remove lime. Cloth so 
prepared will dye and print well. 


50,495—Oct. 17, 1865. George H. REED, Massachusetts. 
Improved preparation and manufacture of dyes and colors. (Product also 
claimed.) Liquid dyes that resist heat and cold and can be preserved indefinitely. 

Soln. of dye with suitable amount of mordant is boiled and evaporated until excess water 
is removed and soln. is saturated, then bottled for market. Dyes can be applied by one bath 
method. Mixtures of colors for silk and wool must be adapted to the two fibers and should not 
ppt. each other. 


54,95 7—May 22, 1866. George H. RrEp, Massachusetts. 


Improvement in the manufacture of dyes and colors. (Product also claimed.) 
Liquid dye comps., stable toward heat and cold. 
Dye comps. are prepared as in 50,495 except that after concentration either glycerin, alcohol, 
pyroxylin, or wood naptha, etc., is added to prevent change. 


60,546—Dec. 18, 1866. Alfred Parar, France. 


Improvement in dyeing and printing textile fabrics and yarms. Developing 
oxidized colors on fiber. 

Chromate of chromium, lead dichromate or manganese chromate, or other suitable insol. 
chromate, is dyed or printed on fiber together with an oxidizable dye such as anilin black, and 
aged, steamed, etc., in the usual way, oxidizing action being delayed and prolonged by in- 
solubility of chromate. Some insol. chromates may also be used for discharge of madder reds, 
erc. 


63,084—Mar. 109, 1867. _ Alfred Parar, France. 


Improvement in dyeing and printing textile fabrics, and in compounds 
therefor. Arsenite of glycerin as oxidizer on fiber. 
Compound for printing or dyeing consists of arsenic and glycerin, coal-tar color, and of 
acetate of Al, of Mg. or other metallic oxide. 


8$3,502—Oct. 27, 1868. I. O. Iversen, Wisconsin. 
Improvement in dyeing textile fabrics with anilin colors. Improved anilin dye 
compound. 


Soln. of dye is spread on smooth non metallic surface and thoroughly dried in air, redis- 
solved in ag. and mixed with 3 parts each of K,Cr,O,, of alum and Na,CO,. 


170,626—Nov. 30, 1875. James Hariety, Massachusetts. 


Improvement in dyeing and printing textile fabrics. (Product also claimed.) 
Dyeing madder on basic anilin colors. 
Anilin colors (basic) are first applied to the fiber on a tannin mordant (Sumac) then goods 
are dyed in madder or indigo. 


186,485—Jan. 23, 1877. Lewis Lrercu, Massachusetts. 
Improvement in preparing anilin dyes. (Product not process claimed.) Soap dyes. 

Two parts soap and 1 part glue or gelatin are mixed with sufficient dye to make desired 
color and incorporated into blocks or cakes of convenient size and shape. 


434 DIGEST OF PATENTS 


242,855—June 14, 1881. Nicholas C. Armanp and Jacques E. Berron, France. 
Dyeing fabrics with anilin colors. (Product also claimed.) Dyeing anilin colors by 
dry process. 


To render anilin colors soluble in benzene or alcohol a special mixture of oil or fat, 
acetic acid or HCl, ether, NH, and K,CO, is incorporated with the dye to form a paste that 
has the required solubility. 


250,302—WNov. 29, 1881. William H. R. Toyrt, New York. (Fabric Orn.) 
Process of preparing colors for ornamenting fabrics. Dye compound. 


An anilin dye is mixed with starch, powd. talc. and acid, dried carefully and pulverized. 


256,596—Apr. 18, 1882. Peter Rerp and John Eastwoop, New Jersey. (Celluloid.) 
Ink for dyeing purposes. Dye compound for topical printing. 


Pyroxylin, preferably that known as “‘nitro-cellulose,” is mixed with a solvent, a coloring 
agent, camphor and alcohol. 


272,499—Feb. 20, 1883. Henry W. Vaucuan, Rhode Island. (Slater.) 
Method of preparing dyestuffs for application to fibrous materials. Dyes not 
readily soluble in mass, prepared for application in finely pulverulent condition. 
Dyestuff such as FUCHSIN and sufficient mordant to fix the color is mixed with oil such as 


paraffine oil and a small quantity of an earth or pulverulent vehicle and thoroughly ground until 
homogeneous and resulting paste incorporated with more earth to desired dilution of dye. 


276,061—Apr. 17, 1883. Alfred M. Meitncxt, New York. 
Dyeing compound. “Garnet Powder,” a mixed dye compound. 


Cornmeal is incorporated with CUDBEAR, INDIGOTIN, acid magenta, and wool orange and after 
first grinding more cudbear added and further ground. 


320,820—June 23, 1885. Rudolf Sruperserc, New Jersey. (Hoops, %.) 
Process of dyeing. Applying dyes on a chrome mordant. 


A portion of mordant liquor described in 320,821 is diluted, fabric soaked therein for 10 
hours washed, etc., and dyed in anilin dye bath. 


320,821—June 23, 1885. Rudolf Srinperserc, New Jersey. (Hoops, %.) 
Mordant. Improved chromium mordant. 
Mordant is same as described in 320,820 in which dichromate and oxalic acid together with 


HNO, and glycerin are boiled in aq. soln. until chromate is reduced, as shown by green color, 
crystals of KNO, removed and NaOH added to liquor which constitutes the mordant. 


334,140—Jan. 12, 1886. John A. van Wrnxtz, Missouri. 
Compound for softening and dyeing broom-corn. : 


Compound contains pure water, 30 gals., alum 0.5 oz., saltpeter 0.5 oz., cider vinegar 1 
quart, diamond dye (green) 1 dram. These are thoroughly mixed and broom corn dipped till 
well saturated, drained, bleached and smoked with burning sulphur to set color. 


342,207—May 18, 1886. Armand MU.wer-Jacoss, New York. (Miiller-Jacobs.) 


Coloring compound. Dye powders containing resinates and colors soluble in benzine, 
turpentine, etc. 
Colophony is boiled with NaOH to form resinate which is mixed with sulfate of Zn or Al. 
or other metal or alk. earth and product separated as powder. ‘These resinates unite with any 
dye sol. in aq. or alc. etc., and the mixture in dry form is claimed by patent. 


404,193—May 28, 1889. Jacob Haun, New York. 
Process of dissolving anilin colors. Water sol. anilin dye comp. that can be mixed 
with paint or varnish. 

In order to incorporate anilin dyes with vegetable oils a water sol. color, such as Fuchsin, 
Bismark Brown, Methyl Violet, etc., is dissolved in hot aq. In a-separate vessel on hot bath 
a vegetable oil, preferably linseed oil, is mixed with o.r of the color soln. boiled and the rest 
of color soln. -added, boiling being continued until water has evaporated. 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 435 


429,131—June 3, 1890. John J. Harr, Massachusetts. 
Process of printing calico. Printing without loss of color in developing bath. 


In printing designs on calico the coloring matter mixed with mordant (tannin) is applied to 
cloth by printing rollers, etc., and steamed to form insol. tannate in fiber, then passed through 
bath of antimony salt at temp. too low to react with tannic acid color lake and finally heated 
outside bath to develop color. Apparatus is described with drawings. 


444,229—Jan. 6, 1891. Robert M. Donovan, Oregon. 
Compound for coloring broom corn. 


Dye compound contains water, 30 gals., anilin dye (green) 2 oz., or more, and weak 
H,SO, instead of vinegar as given in 334,140. The mineral acid strengthens and toughens the 
corn, at the same time making it more susceptible to action of dye. 


482,477—Sept. 13, 1892. Carl J. E. de Hagen, Germany. 
Process of bleaching. Bleaching vegetable and animal fibers. 


Fiber is warmed at 50° in bath of Na,O, containing MgCl,, MgSO, or salts of other bases 
capable of being pptd. by sod. hydrate or carbonate. 


499,687—June 13, 1893. William T. Wuiteueap, Canada. (Dupee, %.) 
Resist-mordant. (Process not product claimed.) Two shade resist printing. 

The resist mordant contains a zinc compound as essential ingredient and after printing 
figure with this resist the fiber is dyed as usual, the effect being a lighter shade of same color 


where resist is applied. If deeper shade is desired in the pattern, the color is also mixed with 
the resist before printing, then cloth dyed as before with same or contrasting color. 


568,344—Sept. 29, 1806. Albert Ganswinpt, Germany. (Boehringer.) 
Mordanting textile fabrics. TLactate of zinc as mordant. 

Material is mordanted with lactate ‘of zinc and dyed by various processes. Colors are not 
so fast as with tannin-antimony mordant, but cost is less, loss of mordant in bath is avoided 


the zinc lactate on fiber will take up its own weight of tannin, and wool dyes, alizarin and re- 
lated colors can be dyed in boiling bath. 


597,401—Jan. 18, 1898. Carl Dreuer, Germany. (Boehringer.) 
Process of mordanting wool. Use of lactic acid instead of tartaric or oxalic in chrome 
mordanting. 


Mordant contains bichromate and H,SO, with just sufficient lactic acid to reduce the 
chromium to lower valence. Advantages are saving of chrome, more brilliant, purer and faster 
colors, softer fiber, regularity of shade and easily controlled process, etc. 


630,199—Aug. 1, 1899. Carl Drener, Germany. (Boehringer.) 


Lactic-acid dye. (Process also claimed.) Lactic acid as assistant in dye bath. 

In preparing dye bath of basic dyes such as Indulin sp. sol. the dye is more readily dis- 
solved in presence of lactic acid or its derivs. 

Title of ‘Lactic acid dye’’ is hardly appropriate. 


650,715—May 29, 1900. Max FremMeErRY and Johannes Ursan, Germany. 
Process of manufacturing cellulose products. Rendering cellulose products glossy. 


CELLULOSE fibers, freshly produced and wound up, are subjected to action of water at 
60-100°, and dried at low temp. not exceeding 40°. 


654,988—July 31, 1900. Leonhard LeprerEer, Germany. 


Process of making acetyl cellulose. 

CELLULOSE is converted into hydrocellulose by heating at 70° in closed vessel with 3 per 
cent H,SO,, or other dil. acid, and adding to 4 parts acetic anhyd. to which must be added a 
little H,SO, if the hydrocellulose was hydrolyzed by another acid. 


659,556—Oct. 9, 1900. August S1rcMuND, Germany. (Badische.) 
Process of dyeing. Dyeing and stoving in one operation. 


Dye such as Rhodamin, Auramin, Methyl Violet, Fast Yellow, Night Blue, etc., is dyed in 
presence of sulfurous acid or comp. that liberates SO, under prevailing conditions in bath. Re- 
sulting colors are level, clear and brilliant and cost of process is reduced. 


430 DIGEST OF PATENTS 


661,985—Nov. 20, 1900. Emil Haussmann, Germany. (Berlin.) 
Process of dyeing. Neutral ammonium salts as assistant in chrome mordanting by one bath 
process. 


Mordanting bath of K,Cr,O, and (NH,),SO, is neutral at first but slowly becomes acid as 
NH, splits off. The latter escapes in part and also aids reduction of chromic acid. The mordant 
is slowly and evenly deposited on fiber and bath may be almost exhausted with no loss of 
mordant. 


663,225—Dec. 4, 1900. Hermann Gurzkxow and Benno Homoika, Germany. (Héochst.) 


Process of dyeing coal-tar colors. Treating dyes to render them fast to washing and 
acids. 


Benzal Violet, Fuchsin, Congo colors, Benzopurpurin 4B, Diamin Scarlet 3B, Fluorescein or 
other dyes containing one or more primary or secondary amino or hydroxyl groups, when 
dyed on fiber can be developed by heating in aq. with 2-amino 3-xylyl 4-TOLUIDIN or other 
aromatic base containing -NH-CH,-linked on both sides to benzene or homologs. 


666,256—Jan. 22, 1901. Max Becxe and Herman Basiicu, Germany. (Héochst.) 


Process of dyeing with basic dyes. Dyeing basic dyes on tannin antimony mordant by 
one or two bath process. 


Basic azo dyes, especially those containing safranins, are dyed on vegetable fibers in neut. 
or slightly acid baths containing neut. salts such as glaubers, and subsequently treated with 
solns. of tannins and Sb. salts, or mixtures of these in dye bath itself or in second bath. 


679,203—July 23, 1901. Maximilian C. L. ALTHAUSSE, Germany. (Sthamer.) 
Process of obtaining hydrocellulose, 


CELLULOSE is heated at 60-70° in dil. HCl and KCIO, in such proportions as to prevent 
formation of oxycellulose. : 


679,204—July 23, 1901. Maximilian C. L. AutHaussk, Germany. (Sthamer.) 
Process of obtaining hydrocellulose. 


CELLULOSE is treated with glac. acetic acid containing free Cl while heating to a non-oxidizing 
temp. (60-70°.) 


692,497—Feb. 4, 1902. Maximilian C. L. AttHaussE, Germany. (Sthamer.) 
Process of making acetyl-cellulose. Dye lakes from acetyl cellulose. 

Hydrocellulose is produced from cellulose by treatment with glac. acetic acid and free Cl 
at 60-70° and acetyl derivs. are obtained from this by mixing with 3.5 parts of glac. acetic and 
3.5 parts acetyl chloride and, when reaction ceases, adding a small amount of H,SO,, heating 
to 60-70°, finally pptg. by diln. and salting out. Soln. of resulting acetyl cellulose in alcohol 
is dyed, soln. diluted and salted out, the lake being voluminous, insol. in aq. after drying, 
transparent or nearly so in thin layers, and of bright colors, suitable for printing. 

Note 679,204, (XXII). 


692,775—Feb. 4, 1902. Maximilian Carl I. AtruaussE, Germany. (Sthamer.) 


Cellulose lakes and process of making same. Colored pastes from acetyl cellulose 
and acetyl cellulose applied as a mordant. 


A conc. soln. of acetyl cellulose is mixed with alc. soln. of Safranin G. or other anilin dye, 
to desired tint, diluted or not, and salted out to form paste. Fabrics are treated with an alc. 
or aq. soln. of acetyl cellulose then with suitable dye to obtain a better diffusion or distribution 
of the color on the fiber. 

Note 679,204 (XXII). 


721,290—Feb. 24, 1903. Mary IL. Fisuer, Missouri. 


Removable coloring-matter for washable fabrics. 


Dye compound contains acid pink, gum senegal, fustic ext., gum arabic and Teeman’s 
soluble blue, thoroughly mixed. When dissolved in water resulting color is dark or black tint. 


734,123—July 21, 1903. Arthur ErcHENGRUN and Theodor BrEcKkEeR, Germany. (Elberfeld.) 
Acetyl cellulose. 


HyYpROCELLULOSE is added to a mixture of 4 parts glac. acetic, 4 parts acetic anhyd. and 
0.2 parts H,SO, (66°), let stand until dissolved as thin liquid and poured into aq. 


ale 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAI, 437 


735,599—Aug. 4, 1903. Hermann Scuraper, Germany. 


Process of mordanting wool, ete. Mordant from trimethyl glycoco) hydroxide, the 
organic acid of vinasse. 


Wool fiber is boiled in bath containing 4.5 per cent fermentation acids and 1.5 per cent 
bichromate, rinsed, centrifuged and while wet placed in 3 per cent acetic acid bath with 2 
per cent Alizarin Cyanin RR, logwood or similar dyes. Other metal salts may be used such as 
Al, Fe, Cu or Sn. Fermentation acids are obtained by fermenting or desaccharifying the vinasse 
with BaO, SrO or CaO, filt’g, neutg. with H,SO,, crystallizing out the K,SO,, and pptg. free and 
combined H,SO, with BaCO,. 


752,804—Feb. 23, 1904. George RowLANpD, Tennessee. (Rowland.) 
Dyestuffs. Soap dyes. 


Neutral or basic anilin colors that dye directly without acid or alk. mordant are incor- 
porated with a “white curd” or neutral soap either at the time the semi-solid soap is being put 
through the crutcher or the solid soap is being milled or the soap may be remelted and dye 
added. Dyed soap is prepared in bars as shown by drawing. Method of using soap is de- 
scribed. 


764,966—July 12, 1904. Otto VENTER, Germany. 
Apparatus for dyeing. 


_ Apparatus is drawn and process described whereby dye liquor is driven by means of a 
pump with optional speed through the material alternately, in opposite directions, by use of two 
three-way cocks, while the pump runs in one direction only. 


776,830—Dec. 6, 1904. William Forcrer, New York. 
Process of cleaning white leather zoods. 


Leather goods are cleaned and bleached by first manipulating in a bath of benzin, oleic acid 
and NH, then a second bath of same with alcohol, again two times in first bath, once more in 
bath of benzin and CaCl, and finally rinsed in benzin. 


8$33,602—Oct. 16, 1906. Carl] IMMERHEISER, Germany. (Badische.) 
Coloring-matter lake. (Process also claimed.) Lakes on alumina base and no other 
metal. ; 


Basic alumina comps. that are basis of lake may be formed before or at same time as lake, 
but must contain an aluminum salt added as such or formed by addition of HCl, HNO,, acetic 
or sulfo cyanic acids. Napthol Yellow S, Acid Green, Eosin, Brilliant Carmine L, or other acid 
dye is mixed with alumina comp. as paste with aq. and a little acid or aluminum chloride or 
BaCl, added to ppt. lake. Amount of added acid must be from 4-17 per cent of that required to 
form a neutral salt. 


$34,739—Oct. 30, 1906. Leon LILIeENFELD, Austria-Hungary. 


Coloring-matter for producing silk-like or pearl-luster effects, 

Viscose in a suitable dissolving medium, mixed with finely colored or noncolored mica, is 
applied to fiber then fixed by dry heat or steaming, acids, salts, etc. Luster can be heightened 
by calendering or embossing, and viscose may be colored without influencing brilliancy of 
mica. Advantages and disadvantages of various binding agents are discussed. 


835,754—Nov. 12, 1906. i Charles Henry, France. 


Process of making a cold dye. Vari-colored effects produced from one dye. 

Two solns. composed (a) of gum lac, colophony and NH, in large vol. alc. and (b) of glue 
and sod. borate in large vol. aq. are combined in any desired proportions with an organic dye 
and exposed to reducing or oxidizing agent such as Cl either as dry gas or in soln. Applied to 
fabric this dye-varnish gives different colors when viewed at different angles. The varnish 
serves as sizing agent and imparts glazed surface. 


839,590—Dec. 25, 1906. Benno Homo.xka and Josef Erser, Germany. (Hochst.) 


Compound of organic colors with fatty acids and process of making same. 
Water-soluble compounds of organic color bases with oleic, sebacic and other fatty acids. 
Methyl Violet 6B, Victoria Blue B base, Rhodamin B base, or other basic dye, is mixed 

with sufficient soft soap to form dye oleate and to conc. hot soln. of latter is added an alkali 

salt of benzyl anilin sulfo, or other aromatic benzyl base. Product is sol. in aq., benzene, fats 
and oils, insol. in ether and especially applicable to shade off printing inks. 


438 DIGEST OF PATENTS 


854,374—May 21, 1907. Harry S. Morx, Massachusetts. (Chem. Prod.) 
Cellulose ester. (Process also claimed.) Cellulose triacetate that retains properties of a 
colloid. . 


CELLULOSE is converted to hydrocellulose and acetylated at normal temp. with acetic acid, 
acetic anhyd. and benzol, thereby conserving the fibrous structure of original cellulose. 


868,008—Oct. 15, 1907. Christoph REeINHOLD, Germany. 
Pulverulent coloring matter for leather. Talc as ingredient of dye compound 
to aid in level dyeing of leather. 
Compound contains soap, tallow, lard, wax, sugar and dye, one part each, also 5 parts olive 
oil and 2.5 parts cocoanut oil and with this mixture talc is mixed and whole is ground to pul- 
verulent mass. 


900,130—Oct. 6, 1908. Hans Torprer, Germany. (Bayer.) 
Process of fixing colors. Fixing substantive colors. 


Substantive colors on cotton, etc., are fixed by treating with (a) Mg salts, (b) stannates and 
alk. agents, in separate baths either in order a—b or b—a. 


905,264—Dec. 1, 1908. Friedrich M. Winter, Germany. 
Process of making lake colors. Lakes with aluminum silicate. ae 

For azo dyes the neut. silicate Al,O; 35iO, is employed, and for basic dyes the acid silicate 
2Al,0,.7SiO,. To produce Orange II, lake an aq. soln. of Al,(SO,), is mixed with soln. of 0.33 
part NaOH, 1.25 parts water-glass (40°), 1.25 parts glauber’s, 1 part dye and 3.7 parts BaCl, 
which are added successively as 10 per cent solns. Aluminum silicate in the form of kaolin, or 
china clay, acts like BaSO, as white substratum but in above comps. it functions differently. For 
basic dyes the silicate is added last. 


941,399—Nov. 30, 1909. Homer Winstow, Rhode Island. (Cassella.) 
Process of dyeing wool. Dyeing by metachrome process. 

Dyebath is made up of 2 per cent suitable dye, 0.5 per cent bichromate and 4 per cent MgsO,, 
goods entered at 26-38° and boiled 1-2 hours. Salts of Ca, Ba or Sr can be used instead of 
Mg. The chromate may be added after the goods are entered. 


964,565—July 19, 1910. Alexander Scumitz, Germany. 
Process of making fatty compounds for use as turkey-red oils. Turkey-Red 
oils mixed with their oxy derivs. 

A suitable oil (long list furnished) is sulfonated, separated and boiled alone or with aq. in 
open vessel until converted to oxy deriv., then mixed in any desired proportion with more of 
original oil and sulfonated again until lime test is negative. After separating from lye, alkali is 
added to give either a neut. or slightly acid or alk. product adaptable to various market re- 


quirements, given in detail by patent. 
Note 861,397 (Gr. XXII). 


982,194—Jan. 17, 1911. George S. Wuitty, New York. (DeVoe.) 
Dyeing compound and process of producing the same. Dye compound in cakes or 
collapsible tubes. - 


Direct dyes or mixtures with acid or basic colors are made into paste with gum tragacanth, 
dextrin, and aq., and 30-50 per cent salt (Na chloride, sulfate, phosphate, etc.) to consistency of 


stiff dough suitable for cutting into cakes or tablets. Or with more aq. and glycerin, etc., is 
prepared as paste for filling collapsible tubes. 2 

a 
983,951—Feb. 14, 1911. Friedrich C. Turts, Germany. (Ho6chst.) : 


Process of bucking or bleaching vegetable fibers dyed with wat dyestuffs. 
Preventing bleeding’ of dyes in bucking process by alk. bromates. 


Liquor for bucking is prepared with 1.2 per cent NaOH and o0.2-0.5 per cent KBrO, and aS 
material is boiled 2 hours or more. x 


995,431—June 20, 1911. Max Becks and Albert Brett, Germany. (Hochst.) 
Process of dyeing half-woolen goods. Union dyeings. 


The wool in mixed wool and cotton goods is first dyed in an acid dye bath containing 
tannin, etc., then tartar emetic, or other metal salt is added to fix the tannin and fiber is dyed 


an 


-, 


ad 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAI, 439 


with a direct dye for cotton. Presence of tannin fixed on wool prevents absorption of second 
dye. 


1,002,118—Aug. 29, 1911. Max Becket, Germany. (Hochst.) 
Process of producing multicolored effeets in spun and woven goods. Dis- 
charge effects by using manganese oxides. 


Cotton fiber (loose laps or twisted yarn) is treated with sol. manganous salt then with strong 
alk. and Mn(OH), pptd. in fiber oxidized to higher oxides by hypochlorite, chromate, or simply 
by air in drying process. Woven with untreated fibers the prepared fibers in acid. dye bath 
liberate oxygen and destroy dyestuffs. Contrast effects are made by use of oxygen fast dyes 
such as thio indigo, anthraquinone vat dyes, etc. 


1,002,635—Sept. 5, 1911. Wladislaus Bratxowsk1, Germany. 
Apparatus for measuring and regulating the concentration of dye liquors. 
Electrical conductivity of selenium cell as control of strength of dye liquors. 
Connection between tank of conc. dye liquor and dyeing apparatus has an automatic ar- 
rangement whereby a constant light source shining through a glass tube containing the dye liquor 


acts upon a selenium cell in an electric circuit the consequent variations of current controlling 
a lever that regulates the supply of dye. 


1,016,295—Feb. 6, 1912. Louis N. Saum, New York. 
Dye or stain. Basic dye compounds to be applied with brush on carpets, rugs, leather, 
wood, paper, etc. 


Mixture consists of wood alc. 94 parts, acetic acid 1 part, tannin 2 parts, shellac 2 parts, 
and basic color 1 part. 


1,019,092—Mar. 5, 1912. Maxim Scuwarz, Austria-Hungary. 


Method of dyeing. Combining substance dyestuffs in neutral gel. form with vegetable or 
animal fiber. 


Dye such as PARA BLUE 2RX in dil. NaOH soln. is mixed with soln. of wheat starch in dil. 
alk., then HCl, H,SO, or NH,Cl, etc., added in sufficient amount to exactly neut. the alkali 
present. The resulting neutral and durable gel. is added to fabric, which is squeezed between 
rolls and steamed. Azo dyes and those of geranin class can be applied in similar manner. 


1,024,668—Apr. 30, 1912. Max Becxt, Germany. (Hdéchst.) 
Production of peculiar color effects on textile fabrics. 
Apparatus is shown whereby a vari-color effect primarily produced on paper is transferred 


to a textile fabric. Paper may be variegated, marbled, veined in two or more colors or with 
relief effects resembling natural patterns. 


1,043,582—Nov. 5, 1912. Carl J. Faiuer, Switzerland. 
Process of preserving and coloring wood. 
Wood is dyed in green or dry condition by immerging in a bath of petroleum distillate (b.p. 


100-105°) and an anilin color and allowing to stand, or subjecting to pressure of 3 atms. and 
temp. above b.p. until permeated. 


1,047,923—Dec. 24, 1912. Gustav C. Dorrr, Germany. 
Process of dyeing vegetable fiber. One bath dyeing and cleaning by use of sod. silicate. 


Vegetable fiber is dyed in a single bath of direct dye containing an alkali silicate which 
cleans the fiber and aids in depositing the dye thereon. 


1,059,740—Apr. 22, 1913. Otto LiEBKNEcHT, and Ferdinand BLUMENTHAL, Germany. 
Making auxiliary mordants containing titanium and glycolic acid. 

Titantic acid is added to an aq. soln. of GLycoxic acid, in presence of alk. or alk. earth 
metals. Other methods of causing combination of two into a compound of value as a mordant 
are given. 


1,059,741—Apr. 22, 1913. Otto LigBKNECHT and Ferdinand BLuMENTHAL, Germany. 
Process of making auxiliary mordants containing antimony and glycolic 
acid. 
Various methods are given for preparing compound of antimony with GLycoLic acid. Aq. 
soln. of GLycoLic acid may be saturated with freshly pptd. antimony oxide in presence of alks. 


440 DIGEST OF PATENTS 


or alk. earth metals, solns. evapd., dried and crystallized. A sodium salt containing 30 per cent 
Sb. is obtained. 


1,066,641—July 8, 1913. | Ansil Morrart, Indiana. (Gates.) 
Process of making dye. Dye compound. 


Six parts dye are dissolved with 1 part agar agar in sufficient water so that when heated to 
homogeneous soln. and cooled a gel is formed. Resulting comp. may be packed in cans, tubes, 
etc., ready for immediate use and is stable under extreme climatic changes, marketing, etc. 


1,139,826—May 11, 1915. John Barrincton, Massachusetts. 
Alkali-free detergent for scouring and dyeing and process of making same. 
Soap dye. 


Detergent consists of a neutral soap, sulfonated castor oil and anilin dye adapted to wool 
and cotton. Goods are boiled with soap dye for 5 min. to cleanse them, then salt is added to 
bath to force dye on fiber. 


1,172,113—Feb. 15, 1916. Alfred Dacuert and Charles Heitz, Germany. 
Coloring medium for concentrated viscous sugar. (Process, not product, claimed). 


Color or dye is dissolved in water with sugar or gelatin or both and conc. in vacuum or air 
at low temp. until sufficiently dry to form uniform tablets. When mixed with viscous sugar 
in preparation of candy, caramels, etc., the tablets readily disintegrate, distribute well, dis- 
solve, and color the medium uniformly. 


1,186,052—June 6, 1916. Rudolf Weeser, Austria-Hungary. 
Process for dyeing of artificial leather. 


The basic fabric is impregnated in the usual way with a layer of nitro-cellulose or cellulose 
acetate, etc., mixed with softening oils and contains in addition a mordant such as Al(OH),, 
silicate or acetate. After a layer of suitable thickness is acquired it is dried and dyed with 
basic anilin dyes in acid bath, the fabric being dyed at the same time. 


1,206,189—Nov. 28, 1916. Maurice N. Arsen, Illinois. 


Composition of matter for sizing and dyeing. Dye compound for hats after they 
have been sewed. 

Glue or similar colloid is hydrolysed and distributed in a dil. alc.-acid or alk. medium (HNO,, 
KCl, HCOOH, KOH) neutralized and used as a non-shrinking sizing comp. which with basic, 
acid or direct colors, etc., in alc soln. may be applied in a dye bath for coloring hats after they 
have been sewed instead of in the braid. Advantages are enumerated. 


1,232,551—July 10, 1917. Carl IMMERHEISER, Germany. (Badische.) 


Coloring-matter lake and producing same. _ [,akes of basic dyes. 

DIAMOND GREEN G. (tetra methyl diamino triphenyl carbinol) or other, is pptd. as lake with 
heavy spar, aluminum sulfate, barium chloride or sodium phosphomolybdate giving VARI COLORED 
lakes that are fast to water and light. 

Note 1,232,552, which uses tungstate salt. 


1,232,552—July 10, 1917. Carl IMMERHEISER, Germany. (Badische). 
Color-lake and producing same. [kes of basic dyes. 

CRYSTAL VIOLET (hexa methyl triamino triphenyl carbinol), or other, and aluminum sulfate, 
sod. carbonate, BaCl, or acid sodium phospho duo deci tungstate or other, are mixed in aq. soln. 
to ppt. dye as lake. Vari-coLorEp lakes that are fast to water and light are produced. 


1,274,046—July 30, 1918. Chas. C. Hurrman, Illinois. (Sunbeam). 
Universal blue dye and method of producing the same. Dye soap. 

A vegetable oil is saponified by alkali in excess, and just before reaction is complete soln. of 
Methylene Blue is added at temp. of 50°, then cooled and product molded. Glycerol may or may 
not be removed. It is claimed that combination takes place between excess alkali and dye to 
form new comp. 


1,274,049—July 30, 1918. Charles C. Hurrman, Illinois. (Sunbeam). 


Universal red dye and method of producing the same. Dye soap. 
Process and materials are same as in 1,274,046 except that Anilin Red or Chrysoidin or 
mixtures of these with each other or with Methylene Blue are employed as coloring agents. 


4 


GROUP XXIII.—APPLICATIONS, BY DYE GROUPS AND IN GENERAL 44I 


1,276,123—Aug. 20, 1918. Joseph A. Scuirrers, Tennessee. 
Dyeing composition. Liquid prepared dyes. 


Dyes as selected are dissolved in water together with anilin oil, or monopole oil, etc., and 
NaCl and preferably also CaCO, (chalk), soln. being as concentrated as possible and put up in 1-2 
oz. bottles. 


1,279,679—Sept. 24, 1918. Fred Frar, New York. 
Soluble dye in sheet form. (Process also claimed). Sheets of bibulous paper as vehicle 
for dyes. 


Paper stock, preferably cotton, and free from Cl or other bleaching agents, is neut. with 
H,SO,, beaten to web or sheet of determined tensile strength, dried, and impregnated with dye 
by immersing in dye bath, drying, etc., whereby color is crystallized on both surfaces of the 
sheet. 


1,283,519—WNov. 5, 1918. Charles C. Hurrman, Illinois. (Sunbeam). 
Method of making universal dyes. Dye soap. 


Process is similar to 1,274,046 and 49, but after forming a large batch it is cast into a block 
and allowed to stand for 24 hours until reaction with dye is complete. Temp. rises from 50° to 
60° during first two hours, then falls slowly. 


1,289,968—Dec. 31, 1918. Sydney M. Toorar, England. 
Dye. Dye wafers. 

The dye composition consists of basic, direct or acid dyes or mixtures, with glue or gelatin 
as carrier, to prevent separate pptn. of dyes, and with a neutralizing agent such as ZnO, or alk. 
carb. to correct acidity of gelatin. Glycerin also may be present. Material after drying is molded 
into wafers of any size or shape. 


1,303,426—May 13, 1919. Edward J. Watt, New York. (Kalmus). 
Dye recovery. Recovering dye from color sensitizing collodion or gelatin emulsions. 

A metallic salt (Al, Sn, Fe, Cr, etc.) and an alkali are added to the dye soln. and resulting 
colloidal hydroxide thoroughly agitated until dye is absorbed. An inert substance such as BaSO, 
may be pptd. in soln. and in this case dye is probably adsorbed. Separated ppt. is dried and 
dye extracted by alcohol or other solvent. Tannin is not suitable as pptg. agent. 


1,307,113—June 17, 1919. Leland C. Carss, Illinois. (Sunbeam). 
Dye-soap. (Process also claimed). Dye soap capable of producing dark as well as light 
shades. 


A quantity of soap is heated to 93.5°, and to this is added sulfonated castor oil in which 
sufficient dye has been dissolved. Mixture is well mixed in crutcher for about 30 mins., placed 
in mold, cooled and formed into cakes, 


1,318,109—Oct. 7, 1919. George F. Ruks, Illinois. 
Composition for coloring meats and meat products. Permitted food dyes as 
coloring agents for meats. 


Orange I, 23 per cent, tartrazin, 2 per cent, and 75 per cent salt are mixed thoroughly. 
Meat is dipped in 2 per cent soln. of the mixture, drained and smoked. 


1,349,265—Aug. 10, 1920. Leland C. Caress, Illinois. (Sunbeam). 
Alkali-proof dye and method of producing the same. Dyes rendered alkali fast. 


Dyes sensitive to alkalies are dissolved in weak alkali (1 per cent) and heated to boil with 
15 parts vegetable oil which may contain as much as 20 per cent mineral oil such as vaseline. 
Saponification that results continues till alkali is exhausted then sufficient NaOH (40°) is added to 
complete the saponification of all the oil. 


1,352,014—Sept. 7, 1920. Eugene L. Maupat. New York. 
Process of dyeing raw silk. Preparing raw silk for dyeing with vat dyes. 


Silk is hardened by treatment in bath with a metallic salt (chromium chloride, iron liquor, 
alum, etc.), washed and dyed in vat, woven, and washed in soap or alk. soln. such as is used 
in degumming silk. 


442 DIGEST OF PATENTS 


1,361,811—Dec. 14, 1920. David J. Brock and Charles C. Hurrman, Illinois. (Sunbeam). 
Dye-soap and mordant. : 


Dye soap is flaked and mixed with a mordant flake containing 20 per cent glaubers and 1 
per cent soda ash during saponification or after working salts into soap. For darker colors more 
mordant flake is used. Mordant flakes may contain CuSO,, tannin and tartar emetic, or other 
metallic salt to mordant or render dye fast. 


1,366,023—Jan. 18, 1921. Edmond Prince, France. (Soc. Chim.) 
Process for preparing cellulose acetate for dyeing. 


Cellulose acetate is treated with relatively conc. soln. of alkali metal salt containing caustic 
alk. 


1,367,930—Feb. 8, 1921. Sydney M. Tootat, England. 
Dye. Protecting cotton portions in dyeing silk or wool garments. 


A weakly acid dye such as Xylene Red or Blue, Acid Violet, etc., gelatin and an organic 
acid are heated in aq. until dissolved, cooled, and molded into forms for market. Gelatin or glue 
acts as a resist to prevent dyeing cotton insertion or lace. 


1,375,919—Apr. 26, 1921. August Lennie, New York. (Pickhardt.) 


Method of Dyeing. Rendering dyeings with basic colors more stable and fast to light. 
Fabric dyed with basic color is after treated with soln. of sod. phosphotungstate or molyb- 
date or the corresponding silico derivs., at common or raised temps. 


1,378,418—May 17, 1921. August Lennie, New York. (Pickhardt.) 


Method of precipitating acid colors. (Product also claimed). Phospho or silico 
tungstic or molybdic lakes. 


One part Acid Green or other acid dye of same class, is mixed in aq. soln. with 2 parts 
BaCl, CaCl,, Pb(C,H,O,),, or other suitable salt, and sufficient sod. phospho tungstate to ppt. 
whole as lake. Molybdenum is an equivalent for tungsten and silicon for phosphorus in above 
complex salt. 


1,378,882—May 24, 1921. Arthur L1nz, New York. (Chem. Found.) 
Process of producing tungsten lakes. Phospho tungstic lakes of basic dyes. 


Basic dyes such as Crystal Violet are pptd. in dil. acid soln. with sodium tungstate and 
HNa,PO, in proportion of 4.5 lbs. and 8 lbs. to 1 lb. of the phosphate. Any substratum for the 
lake may be used and any soluble comps. of the pptg. agents. 


1,383,092—June 28, 1921. John H. Fresicer, New Jersey. 
Composition for dyeing animal fiber. 


Compound contains anilin color, an organic acid such as oxalic, tartaric or citric, (less than 
5 parts) and glaubers salt as diluent. 


1,413,026—Apr. 18, 1922. Charles C. HurrMan, Illinois. (Sunbeam.) 


Dark dye combined with soap and process of producing the same. (Product 
not claimed). Dye soap for producing dark shades. 


Process is similar to 1,274,046, etc., except that excess dye and alkali are used and after 
equilibrium is reached the portion of unabsorbed dye is brought into further reaction by adding 
water to the mass and heating to drive off part of the water. Resulting soap contains more 
dye and will produce darker shades. ; 


1,414,029—Apr. 25, 1922. Arthur Linz, New York. (Chem. Found.) 
Method of dyeing. Rendering dyeings with basic colors more permanent and fast to light. 


Textiles, leather, etc., are treated with soln. of soluble comps. of phosphorus (or silicon) 
and a difficultly fusible metal (tungsten, molybdenum) and an acid capable of freeing the phos- 
phoric, silicic, tungstic, or molybdic acids from their salts (such as HCl, H,SO,, acetic, etc.), then 
dyed with basic, or other, dyes. 


1,414,030—Apr. 25, 1922. Arthur Linz, New York. (Chem. Found.) 


Method of dyeing. 


Process differs from 1,414,029 in first dyeing the fiber then treating with phosphotungstic 
acid, etc., as claimed. 


Fa 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 443 


1,414,031—Apr. 25, 1922. Arthur Linz, New York. (Chem. Found.) 
Method of dyeing. 


Patent differs from 1,414,030 in making specific claims for basic dyestuffs. 


1,415,023—May o, 1922. John M. Donouve, New York. (Eastman.) 
Process of making cellulose ethers. 


Cellulose is soaked in 18 parts 50 per cent NaOH at 18° for 3 days, o.5 parts powd. NaOH 
added, whole squeezed to 4.5 parts, charged into an autoclave with 3.75 parts ETHYL chloride and 
heated 24 hours at 90-170”. 


1,425,364—Aug. 8, 1922. John F. Briccs, England. (Amer. Cell.) 
Treatment of cellulose acetate products. Rendering cellulose acetate products amen- 


able to dyeing. 


Filaments, threads or fabrics of cellulose acetate, having a lower degree of acetylation than 
triacetate, are superficially saponified at 70-75° with NaOH (3-5 per cent of dry wt. of cellulose 
acetate) or other, so as to lose not more than 5 per cent in weight. 


1,450,463—Apr. 3, 1923. Alfred Tuauss and Alfred GUntHER, Germany. (Bayer.) 


Sulphurized compound of phenols. Mordants for basic colors on cotton fiber. 


2-Chlor PHENOL dissolved in about equal parts 30 per cent NaOH, is refluxed with about 0.4 
parts S, resinous product sepd., dissolved in about 0.6 parts Na,CO, in hot aq., salted out, and 


dried in vacuum until solid and pulverulent. Other phenols, cresols, anilin and halogen or other 


derivs. are claimed. Method of appln. to fiber is given. 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES. 


The group of finished products other than dyes consists of the following sub- 
classes, which are indicated in the abstracts and indexes by letters in parentheses, 
as shown. No claim is made that the list of abstracts in these subgroups is complete. 


Explosives. Symbol (e). Photochemicals. (p). 
Flavors and Perfumes. (f). Plastics. (pl). 
Medicinals. (m). Tannins, synthetic. (2). 


SUBGROUP (e).—EXPLOSIVES. 


1,292,266—Jan. 21, 1919. Rasik L. Datra and Phuldeo S. Varma, India. 
Process of producing trinitro compound from phenol, Trinitro phenol or trinitro 
cresol. 
PHENOL or CRESOL, is digested on sandbath with a little more than equimol. of conc. H,SO, 
to form sulfo acid, steam distilled to removed unchanged phenol, and mixed nitrous gases (N,O, 
and N,O,) from electric are or reduction of HNO,, etc., passed through the purified sulfo acid. 
Yield of trinitro phenol is 80 per cent and cresol deriv. is 70 per cent. 


1,297,524—Mar. 18, 1919. 
Harry I. WoLienBERG and Charles A. BicELow, New York. (Aetna.) 
Process of purifying nitro-aromatic compounds. 
TRINITROTOLUENE or related nitro comp. in finely divided state is washed below 30° with 
5-10 per cent Na,SO, or other alk. sulfite, various methods of bringing about thorough contact 
of solvent with the nitro comp. being outlined. 


1,309,559—July 8, 1919. Clifford A. Woopsury, Pennsylvania. (du Pont.) 
Process of refining crude trinitritoluol and other crude aromatic nitro 
compounds. Refining crude nitro comps. with a cheap solvent for impurities. 

Crude trinitro ToLvoL or related comp. is mixed thoroughly with 2 parts 93 per cent H,SO,, 
filt, washed with more acid then with aq. and rinsed with weak alk. Or treatment with acid may 
take place entirely on filter, the object being to shorten the contact as much as possible to avoid 
substantial dissolution. Stronger acids have higher refining value and weaker acids such as 
70 per cent have low value. 

29 


444 DIGEST OF PATENTS 


1,309,577—July 8, 19109. Fletcher B. Houmes, New Jersey. (du Pont.) 
Process of obtaining nitro compounds. Nitro products from petroleum. 


Apparatus is shown and process described whereby crude PETROLEUM which contains nitrifi- 
able components is nitrated by the counter current method, being fed continuously through a 
spray at the bottom of a tall narrow nitrating vessel where it meets a descending current of 
nitric or mixed acids, so regulated that spent acid may pass out at the bottom and nitro products 
together with unchanged petroleum are drawn off at the top, pass through a condenser and are 
fractionated. Nitro products dissolved in spent acids and in petroleum are conserved. 


1,520,076—Oct. 28, 1919. David B. Macponatp and Jackson Catvert, England. (MacDonald.) 


Manufacture of nitrophenols. Nitrophenols from benzene using HgNo, and CO, as 
catalyzers. 


BENZENE is mixed with 2.25 parts HNO, (1.42) and a little aq. in which o.1 parts Hg have 
been dissolved and equimol. CO, is passed in at 2 atms. pressure and temp. of 40-50°, during 
period of 6 hours. Upper layer of liquid consisting of 2.4-dinitro phenol, some nitro-benzene and 
traces of 2-nitro phenol, is drawn off and fractionated. Or mixture may be separated by dis- 
tillation with steam. By another method the CO, gas may be charged with HNO, vapor from 
separate vessel containing the bulk of the HNO,. Volatile vapors are conserved. 


1,320,077—Oct. 28, 1919. David B. Macponatp and Jackson Catvert, England. (Macdonald.) 


Manufacture of nitrophenols. 


Process is similar to 1,320,076 using current of oxygen, of air, or of mixture of these and 


of CO,. 


1,325,168—Dec. 16, 1919. Lucien J. J. Perrucue, France. 
Process for the production of nitro compounds. Nitro comps. using N,O, and 
oxygen. 


BENZENE and 2 parts N,O, with 1 per cent aq. below 20° are treated in an autoclave at 4 
kg. pressure with oxygen or air for 6-ro hours, excess N,O, distilled over and HNO, separated 
from nitro compound by known methods, or treated with H,SO, to form dinitro deriv. Materials 
such as ANISOL are dissolved in CCl,, etc., to moderate violence of reaction. Yield is 30 per 
cent ortho and 7o per cent para nitro anisol. 


1,826,947—Jan. 6, 1920. John MarsuHaui, Pennsylvania. (du Pont.) 


Process of making hexanitrodiphenylamin. Hexanitrodiphenylamin from dinitro 
comp., by use of mixed acid in iron vessels. 

One part 2.4-dinitro DIPHENYLAMIN is mixed at 70° with 5 parts mixed acid (30 per cent 
HNO,, 55 per cent H,SO, and 15 per cent aq.), temp. raised to 80-90° for 1 hour, cooled to 
30° and solid 2.4.2’.4’-tetranitro deriv. separated by filtn., is further nitrated in mixed acid (20 
per cent HNO,, 75-80 per cent H,SO, and 5-0 per cent aq.) at 70° then 80-90° for 1-2 hours. 


1,370,067—Mar. 1, 1921. Charles M. Stine, Delaware. (du Pont.) 


Process of making explosive compounds and product thereof. An explosive of 
aromatic series with nitro groups in nucleus and plurality of nitrate groups in side chain. 


BENZENE, or homolog having a side chain, such as methyl ethyl benzene, is chlorinated until — 


theoretical increase in weight desired and in such way that Cl is attached to each primary and 


secondary carbon of the side chain, then nitrated with mixed acid by usual procedure, until dinitro 
comp. is obtained, heated with pure aq. under 20 lbs. pressure until Cl in side chain is re- 


placed by OH, separated and further nitrated with mixed acids to substitute NO, for OH in side 
chain. List of possible products is given. 


1,380,185—May 31, 1921. Theodore J. Brewster, New Jersey. — 


Process of nitrating benzol. Dinitro phenol by nitrating and oxidizing benzene. 


Apparatus is shown wherein BENZENE and 45-55 per cent HNO, containing a catalyst (Hg 3 
NO,) pass continuously at 50-60° through reaction vessel, cooling device and filter in closed — 


circuit. Benzene is supplied as needed, fumes are collected, acid is withdrawn, cone. and re- i 
turned to vessel. a 
1,390,378—Sept. 13, 1921. Erwin Ort, Switzerland. (Faust.) a 


Explosive and process of making same. Cyanure triazid, a superior priming agent. 
Finely pulv. cyanuric chloride, 6.2 gr., is added gradually during 1-2 hours, to soln. of 
7 gr. sod. azid in 70 cc. aq., cooling and stirring strongly, let stand 2-7 hours while cold, filt. 


sc 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 445 


by suction, etc. Yield is 83.5 per cent, with 9-10 gr. azid it is 91 per cent, with a second treat- 
ment of 2-3 gr. azid yield is 92.6 per cent and one crystn. will give pure azid. Sod. azid in 
excess can be recovered. Advantages of cyanure triazid as priming agent are given and graph 
comparing its effectiveness with mercury fulminate, lead and silver azid, etc. 


1,398,998—Dec. 6, 1921. George B. Brapsuaw, Connecticut. 
Process of producing phenols. Dinitro phenol from dinitro chlorbenzene. 


Dinitro chlor BENZENE, § parts, with 1.75 parts Ca(OH), and roo parts aq. are charged into 
a steam jacketed autoclave, temp. raised until pressure is 10 lbs. where it is held for 3 hours, 
then batch is run into a tank and sufficient HCl added to make Ca salts of dinitro phenol soluble 
(0.1-0.5 parts), filt. etc. 


1,401,6831—Dec. 27, 1921. Robert C. Moran, Pennsylvania. (du Pont.) 


Process of preparing dinitrodiphenylamin. Dinitro diphenylamin formed in absence 
of solvents. 


2.4-Dinitro chlor BENZENE, ANILIN and Na,CO, or NaHCO,, in mol. proportions, are stirred 
in an iron container while temp. is raised to g0-100° and held until reaction is complete, or 
about 1 hour. Reaction runs smoothly, co, is evolved, dinitro diphenylamin is in pulverulent 
condition and extraction with water will remove NaCl leaving product of m.p. 150—-152°. 


1,417,368—May 23, 1922. Tenney L. Davis, Massachusetts. (U. S. Govt.) 


Mercury nitrate as a reagent for the preparation of nitrophenols. Nitro- 
phenol mfr. by controlled process with larger yield. 


BENZENE, or homolog, and HgNO, in mol. proportions will react with HNO, in the cold to 
form a black solid complex which when treated with hot HNO, will form oxide of nitrogen, 
Hg(NO,), and 2.4-dinitrophenol or picric acid according to conditions. The mercury reagent 
enters fully into reaction and does not act as a catalyst as supposed heretofore. 


1,450,675—Apr. 3, 1923. Charles M Stine, Delaware. (du Pont.) 
Process of separating isomeric trinitrotoluenes. 


The crude mixture of isomeric trinitro TOLUENES in the form of fine grains or porous pellets 
is placed on false bottom filters and by means of a distributor sufficient CCl, (about 4.5 parts) 
to dissolve undesired isomers is run over this layer. Trinitro xylol can be purified in similar 
manner and ethyl alc., xylol, benzol, toluol, trichlor ethylene, solvent naphtha or mixtures of 
these may be employed as solvents. 


SUBGROUP (f).—FLAVORS AND PERFUMES. 


319,082—June 2, 1885. Constantin FauHiserc, New York. (List.) 


Manufacture of saccharine compounds. (Product also claimed.) Saccharin, or 
benzoic sulfinid, C,H,O,SN. 

TOLUENE, or deriv., is sulfonated to form two isomeric sulfo acids, neut. with CaCO,, salt 
in filtrate converted to Na salt, soln. evapd., residue thoroughly dried then treated with PCI, 
to form isomeric solid and liquid rotuENE sulfo chlorides which are centrifuged and liquid 
chloride warmed with (NH,),CO, or NH,OH to give TOLUENE sulfamid. This is separated and 
oxidized in alk. soln. with PbO, or other to form salt of saccharin which with acid separates 
saccharin. Recovery of by-products is described. 


464,772—Apr. 3, 1900. Albert VertEy, France. (Soc. Ang. Franc.) 
Process of making sulfonates. Pyridin chlor sulfonate for mfr. of vanillin or similar 
comps. 


Two mols. PYRIDIN are mixed in 6.3 parts CS, with 1 mol. SO,CIOH, then 1.11 parts clove 
oil poured in and CS, distilled off. Residue is made alk. to turmeric, pyridin freed, and potas- 
sium eugenol sulfo separated and boiled with 10 per cent KOH to convert to iso comp. which 
is oxidized in aq. at 60° by current of ozone or by electrolysis to vanillin sulfo, K salt, sep- 
arated from soln. by acid, heated to 80-100°, and purified as the bisulfite comp. Other pyridin 
chlor. sulfo comps. with phenolic derivs. are claimed. 


489,72S8—Jan. 10, 1893. Joseph BERLINERBLAU, Russia. (von Heyden.) 


Paraphenetol carbamide and process of making same. A substitute for sugar. 


4-PHENETIDIN, 2 mols., or ANISIDIN, in 2-3 parts benzol or toluol as solvent, is added to 2.5 
parts 20 per cent COCI,, 1 mol., also in benzol soln., the phenetidin HCl filt. off and 2 mols. 


446 DIGEST OF PATENTS 


NH, added to liquid, containing 1 mol. phenetidin carbonyl chloride, to convert this into 4- 
phenetol carbamid. 


548,719—Oct. 29, 1805. 7 Pierre P. Monnet, France. 
Process of making rhodinol. Rhodinol or oil of roses derived from oil of pelargonium 
(geranium). 


Oil of PELARGONIUM is digested at 100° for 2 hours with 0.4 parts 37.5 per cent alc. KOH 
to saponify ethers, neut. acids, destroy aldehydes, etc., the alc. removed by distn., oil thoroughly 
washed and fractionated 3 times, fraction between 115-125° treated with glac. acetic acid, or 
anhydride, for 12 hours at 180° (proportions of 1.54:1) washed with hot aq., the acetic ether 
dried and distilled in vacuum (118-122° and 10 mm.), saponified by alc-KOH, washed well, 
dried, and rectified under reduced pressure. Valuable by-products are recovered. 


551,131—Dec. 10, 1895. Prosper Monnet, France. 


Process of making toluenesulfochlorids. Improved process for toluenesulfochloride 
using chlor sulfonic acid. 
TOLUENE is run slowly into 4 parts chlor sulfonic acid at 0° and kept below 5° for 12 hours, 
diluted with ice and valueless solid para sulfo chloride separated from the liquid ortho isomer 
by cooling to —zo0° and filtg. Yield is 60 per cent tech. product. 


581,053—Apr. 20, 1897. Fritz Acu, Germany. (Boehringer.) 


Process of obtaining cinnamic aldehyde. Cinnamic aldehyde in high yield by 
shorter and cheaper process. 

BENZALDEHYDE, 5 parts, and 4 parts ACETALDEHYDE are dissolved in 1o parts alcohol, cooled 
to 10° and io parts soda lye slowly poured in. After 15-20 m. soln. is dild., oil extracted with 
ether, which is recovered and oil distilled in vacuum. Pure cinnamic aldehyde distils at 120-125° 
and 11 mm. An 8o per cent yield may be obtained. With soda or potash, basic sod. phos- 
phate, calcium or barium hydroxide yields are not so good. 


648,568—May 1, 1900. Joseph Kortscuet, France. (Soc. Chim.) 
Process of making toluene sulfochlorid. 


TOLUENE is run gradually but rapidly with constant stirring into 3-5 parts chlor-sulfonic 
acid free from SO,, at temp. of 5-35°, preferably 10°. Freedom from SO, makes it possible to 
use chlor sulfonic acid at over 5° temp. with larger yield of product and at lower cost for cool- 
ing agents. 


658,769—Oct. 2, 1900. Hugo and Ernst ErpMANN, Germany. (Berlin.) 
Methyl ether of anthranilic acid and process of making same. 


ANTHRANILIC acid in 5 parts methyl alc. is sat. with HCl gas. The soln., which boils, is let 
stand several hours, alc. distilled off, and methyl ester of anthranilic acid is separated as an 
oil by adding aq. Na,CO,, washed and distilled in vacuum. 


Silas 


667,861—Feb. 12, 1901. Augustus BiscuueEr, Switzerland. (Basle.) 


Proecess of producing ehlorids of aromatic sulfonic acids. 2-Toluene sulfo 
chloride for saccharin mfr. 
2-Toluene sulfinic acid, or ester of 2-benzoic sulfinic acid, is dissolved in dil. NaOH and Cl © 

introduced until oily chloride is formed. Or Cl may be passed into suspension of sulfinic acid 

in dil. HCl. % 


692,598—Feb. 4, 1902. Albert Baur, Germany. (Thann.) 
Process of separating orthotoluenesulfochlorid. Toluene sulfo chloride separated 
as the Mg. salt. 

TOLUENE is sulfonated in fuming acid at 14-16°, diluted and 4-sulfo acid filt. off, again 
diluted and 2-sulfo acid pptd. at —5°, separated, freed of H,SO,, soln. ‘sat. with MgCO,, evap., 
heated at 110-120°, pulv. Mg. salt added to 5 parts SO,OHCI below 18°, diluted with ice and 
pptd. 2-toluene sulfo chloride filt. out. 


‘ 
4 
i 
> y 
L 
2 
2 
692,863—Feb. 11, 1902. Joseph Korrscuet, France. (Soc. Chim.) 4 
Substituted sulfinid and process of making same. (Product not claimed.) 4-Amino 
benzoic sulfinid produced directly from 4-nitro toluene sulfamid. 
4-Nitro 2-TOLUENE sulfamid is dissolved in 10 parts of aq. containing 6.45 per cent sulfur 
and 12.9 per cent NaOH, boiled some hours, made acid, and ppt. extracted with ether. 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 447 


714,931—+4ec. 2, 1902. Georg Merrutinc, Germany. (Hochst.) 
Hydrobenzaldehyde and process of making same. 2-Iso propyl 4-methyl hexahydro 
benzaldehyde, or other. 


Hydro BENZYL amin bases are transformed by oxidizing agents into hydrobenzylidine comps. 
that are decomp. by heating with acids. Patent gives reactions in extended detail. 


743,305—Nov. 3, 1903. Georg Mertinc and Robert Wetpr, Germany. (Hochst.) 
Trimethyl-cyclohexenoncarboxylic-acid ester and process of making same. 

A parent material for perfumes. 

Ethyl ester and iso propylidene ethyl ester of aceto acetic acid, 1 mol. each, are condensed in 
alc. soln. by means of 1 atom metallic Na. by standing several weeks at low temp. Sod. ethyl 
carbonate separates, soln. is neut. with dil. H,SO,, alc. distilled off in vacuum and ester re- 
maining as layer of oil extracted with ether, dried, rectified, etc. 


804,682—Nov. 14, 1905. Rudolf J. M. Sommer, Austria-Hungary. (Fritzsche.) 
Process of making protocatechuic aldehyde. Material for mfr. of vanillin, etc. 


HELIOTROPIN in alc. soln. mixed with excess NaHSO, and aq. is heated under pressure of 
not more than 12 atms. and below 190°. Variations of method are given. 


1,329,272—Jan. 27, 1920. Elnathan K. Netson, Maryland. (U. S. Govt.) 
Vanillyl amin, vanillyl, acyl amid, and production thereof. 

_ VANILLIN in alc. soln. is treated with NH,OH.HCl and Na,CO, in warm place 24 hours, 
ale. evapd., aq. added to ppt. vanillin oxim which in alc. soln. is reduced with sod. amalgam 
while glac. acetic is slowly added to maintain acid reaction. To 2 mols. of purified vanillyl 
amin (dried at 110°), suspended in dry ether, 1 mol. acyl chloride is added, heated gently, aq. 
and HCl added and soln. extracted with ether, which is washed with dil. Na,CO, and evapd. 
Amids may be formed from a large number of organic acids, acid chlorides and acid anhydrides. 


1,5345,649—July 6, 1920. Andre Weiss, France. (Soc. Chim.) 
Process for the manufacture of oxyaldehydes and of their ethers. Vanillin 
or 2-anisol 4-aldehyde, or other. 

GUAIACOL, or other aromatic oxyaldehyde, is mixed with FORMALDEHYDE in mol. proportions 
in alc. soln., alc. HCl and 0.5 mol. 4-nitroso dimethylanilin added, then heated at 100° several 
hours while HCl gas is bubbled through soln. Soln. is cooled, made alk. with dil. NaOH so 
that 4-amino dimethylanilin may be removed with ether, etc., then made acid and vanillin ex- 
tracted by ether, etc. 


1,372,434—Mar. 22, 1921. Jacob M. Jouztin, New York. (Semet-Solvay.) 
Process of forming diphenyl oxid. Diphenyl oxide made in one operation. 

BENZENE sulfo, Na salt, and about 60 per cent of alkali required to combine with all the sul- 
fonate, is heated in closed vessel until aq. ceases to form then heated at 420° to condense 
tesidual sulfonate with phenate to form diphenyl oxide, which distils off. 


1,418,904—June 6, 1922. Florentin Bripaup, France. (Soc. Chim.) 
Process for the manufacture of aromatie oxaldehydes. Vanillin from guaiacol. 

GuAIACOL, with 2.5 parts METHYLAL (dimethyl glycol) and nitroso DIMETHYL ANILIN derived 
from 2 parts dimethylanilin, in 12.5 parts methyl alc. are heated at 100° for 1-2 hours while HCl 
gas is bubbled through soln. Alcohol is removed by distillation and vanillin extracted from 
residue with benzene or ether, and purified. Methylene chloride, sulfate, diacetate or other, can 
replace methylal. 


1,427,400—Aug. 29, 1922. Chauncey C. Loomis, New York. (Semet-Solvay.) 
Process of producing salicyl aldehyde. 

Saticyiic acid, 10 parts, is warmed with 8 parts borax, 10 parts boric acid and 3o parts aq. 
to form acid sod. boro disalicylate, cooled to 15° and 20 parts NaHSO, added with stirring and 
cooling. Fifty parts 10 per cent sod. amalgam are then added at 15°, Hg separated and soln. 
evap. to cryst. salts., filt., 200 parts aq. added and aldehyde distilled off. When formed in 
presence of excess alk. sulfite the sulfite addition product prevents decomp. of the aldehyde. 


448 DIGEST OF PATENTS 
SUBGROUP (m).—MEDICINALS. 
254,098—Feb. 21, 1882. Wilhelm PickHarpt and Hermann ENDEMANN, New York. 


Manufacture of chinoline. Purification of crude quinolin. 
QUINOLIN, crude, prepared according to Skraup pat. 241,738 is pptd. as tartrate, filt. base 
freed by alkali, distilled with steam and dried. It is colorless when exposed to air in soln. 
Addition to 241,738 (Gr. XXII.). 


273,498—Mar. 6, 1883. Otto Fiscuer, Germany. (Hdchst.) 


Process of preparing oxyhydro ethyl chinoline. (Product also claimed.) 

QUINOLIN is converted to mono sulfo acid by heating at 100° in fuming H,SO,, neut. with 
lime, converted to dry Na salt, which is fused in 2-3 parts NaOH until converted to Na salt 
of oxy-quinolin and product thrown out of diluted melt with excess HCl. Two isomeric alfa and 
beta oxy quinolins are sepd. by crystn. from aq. The oxy hydro and alkyl derivs. are derived 
by usual methods of reduction with Sn and HCl and treatment with alkyl halides. 


276,796—May 1, 1883. Otto FiscuHer, Germany. (Hochst.) 
Preparation of oxyhydro-methyl chinoline. (Product also claimed.) Oxy methyl 
quinolin. 


QuUINOLIN sulfo is converted to 1-oxy deriv. as in 273,498 and this is heated with 1 mol. 
METHYL iodide to form hydriodide of 1-oxy methyl quinolin, which base is pptd. by NaOH. 


282,488—Aug. 7, 1883. Alexander BOuHRINGER, Germany. 
Method of producing monalecylised hydro-bases. Methyl hydro quinolin base. 


QUINOLIN, lepidin or other tertiary base is condensed with METHYL chloride to form chlor 
methyl quinolin, then reduced to methyl hydro quinolin base. 


295,825—Mar. 25, 1884. Zdenko H. Sxraup, Austria-Hungary. (Badische.) 
Manufacture of parachinanisol. (Product, not process, claimed.) Parachinanisol. 

4-Amino ANISOL and o.8 parts 4-nitro ANISOL, nitrobenzene, or similar nitro compound are 
refluxed with 5 parts GLYCERIN and 2.8 parts H,SO, (1.848) at 140-155°, and product recovered 
by distn. with steam from alk. soln. 


307,399—Oct. 28, 1884. Ludwig Knorr, Germany. (Berlin.) 
Preparation of dimethyl-phenyl-oxypyrazol. (Product, not process, claimed.) 
Dimethyl phenyl oxy pyrazol, m.p. 115°. 
Aceto ACETIC ester is condensed with 1 mol. PHENYL hydrazin then heated to 1c0-150° 
whereby alcohol is eliminated, again heated with methyl chloride, etc., to form the dimethyl 
deriv. 


318,662—May 26, 1885. Ernst W. R. ScHrOTER, Germany. 
Topical remedy. Ichthyol sulfonic acid. 

Oils containing sulfur in natural combination, such as schist oil, are sulfonated in 3 parts 
conc. H,SO, Product can be further sulfonated. 


322,940—July 28, 1885. Theodor Krempr, Germany. (Chem. Fab.) 


Manufacture of iodoform, bromoform, and chloroform. 
ALCOHOL, aldehyde or acetone, is treated with potassium iodide or other alkali or alkali 
earth halide to form iodoform, chloroform, or bromoform. 


343,803—June 15, 1886. Constantin FAHLBERG, New York. 


Medicated benzoic sulphinide compound. (Process also claimed.) Benzoic sulfinid 
compounded with organic alkaloid to neutralize bitter taste of alkaloid. 
Quinine, or other alkaloid is neutralized in alc. or aq. soln. with BENzoIc sulfinid to form a 
salt neutral to litmus. 
. Note 319,082 (Gr. XXIV f.) 


428,286—May 20, 1890. Carl Paar, Germany. (Kalle.) 
Phenyldihydroquinazoline. 


2-Nitro benzyl ANILIN* is refluxed with 20 parts conc. FORMIC acid or treated in benzene soln. 


with sodium formanilid to form 2-nitro BENZyL formanilid which is reduced in alc. soln. with 
Sn and HCl. The SnCl, double salt, the HCl, the base and derivs. are claimed. 


* For preparation of anilin comp. see Lellmann and Stickel, Ber., 19, 1604. 


CS EO ig) ee 


PPL aie 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 449 


464,861—Dec. 8, 1891. Gustav Expert, Germany. (Hochst.) 

Process of making phenylethylmethylpyrazolone. (Product also claimed.) 
Phenyl ethyl PyRAZOLONE with equal part ETHYL iodide is heated in enameled vessel under 

pressure to 150° for 12 hours, purified and HCl salt formed. Product is sol. in usual solvents, 


except ligroin, deliquesces, with nitrous acid gives nitroso comp., with FeCl, a double salt (R). 
It is a homolog of antipyrin and may be used like this as a medicine. 


466,70S—Jan. 5, 1802. Josef ZrEGLER, Germany. (Lembach.) 
Process of preparing oxychinoline sulphate. 

2-Amino PHENOL 4-sulfo and equimol. 2-nitro PHENOL 4-sulfo are refluxed with GLYCERIN and 
H,SO, (60°), diluted and product pptd. by soda distilled with steam and again refluxed with 
2 mols. dilute H,SO, (66°) then distilled in vacuum. 


492,868—Mar. 7, 1893. Hermann JanssEN, Germany. (Bayer.) 
Salicylic-acid compound. (Process also claimed.) Acetyl 4/-amino phenyl salicylic acid. 

4'-Nitro phenyl saLicyLic acid is reduced with Sn and strong HCl in presence of alcohol. 
H,SO, (60°), diluted and product pptd. by soda, distilled with steam and again refluxed with 
H,S to remove Sn, soln. pptd. by Na,CO,, ppt. sepd. and acetylated. 


495,124—Apr. 11, 1893. Adolf SprecEL, Germany. 
Sulphur compound. (Process, not product, claimed.) Ichthyol sulfonic acid. 

Mineral oil distillate is purified by alk. and acid, residue treated with fuming H,SO, (10 
per cent SO,), soluble portion pptd. by salt and purified from sulfones, etc. 


501,235—July 11, 1893. Bruno R. Se1Fert, Germany. (von Heyden.) 
Creosote compound. Carbonic acid ethers of creosote. 


CREOSOTE is dissolved in alkali and treated with PHOSGENE, or is heated with ethers of car- 
bonic acid, or the carbonyl chloride of creosote is treated with creosoted alkali. 


503,066—Aug. 8, 1893. Hermann Tuoms, Germany. 
Salicylate of para-tolyldimethylpyrazolon. (Process also claimed.) 

4-Tolyl HyDRAzIN is heated with acetic ether, then with methyl iodide and methyl alcohol to 
form 4-tolyl dimethyl PyrazoLonr which is melted with saLicyLic acid. 


503,748—Aug. 22, 1893. Leonhard LEDERER, Germany. (Boehringer.) 
Amido-crotonylanilid and process of making it. 
Acetyl acetanilid is treated with NH,. 


512,590—Jan. 9, 1804. Gerhard N. Vis, Germany. (Dahl.) 


Orthooxyethyl-alpha-benzoylamido-quinolin. (Process also claimed.) Benzoyl 
s-amino 8-ethoxy quinolin,* m.p. 208°. 
5-Amino 8-ethoxy QUINOLIN is boiled with 2 parts BENzZoyL chloride, mass boiled with aq. 
and'NH, added. Or these are mixed cold in dil. NaOH to fix HCl set free, then NaOH in 
excess added until odor of benzoyl chloride disappears. 


513,204—Jan. 23, 1894. Ernst W. R. ScHrotrer, Germany. (Cordes.) 
Process of making pure sulfonin compounds. Purifying ichthyol sulfo acid and 
other sulfo comps. from mineral oils. 
Soln. of crude sulfo acids from mineral oils made as in 318,662 is acidified with HCl until 
color becomes paler. The desired sulfo acids crystallize and settle to bottom of liquid, are 
separated and purified by recrystn. 


533,718—Feb. 5, 1895. Jacob Meyer, Germany. (Bayer.) 
Tannin compound. (Process also claimed.) Acetyl and diacetyl gallic acid. ; 

Dry TANNIN is mixed with 0.5 parts glac. acetic and 1 part acetic anhyd. and heated at 
130-140° from 6-7 hours, then poured in thin stream into aq. and stirred to convert into light 
yellow powd. Instead of tannin other gallic derivs. and for acetic anhyd. other acid anhyd. may 
be employed. 


* For description see J. prak. Chem., new vol., 45, 541. 


450 DIGEST OF PATENTS 


537,841—Apr. 23, 1895. Joseph F. von Merino, Germany. 
Process of making ethers of paraoxyphenylurethane. (Products also claimed.) 
Acidyl derivs. of 4-oxy phenyl ethyl urethane. 


4-Oxy phenyl ethyl URETHANE mixed with acetic anhyd. is heated under pressure. Glac. 
acetic or acetyl chloride may replace the anhyd. and propionyl and other acidyl derivs. are also 
claimed. 


541,489—June 25, 1895. Joseph F. von Merrine, Germany. 
Acidyl compound of para-oxyphenylurethan ethers. (Process also claimed.) 
Acidyl derivs. of esters of 4-oxy phenyl ethyl urethanes. 


Process is similar to 537,841 using 4-oxy phenyl ethyl URETHANE esters as materials to be 
acidylated. 


543,214—July 23, 1895. Wilhelm Mayert, Germany. 
Aromatic glycocol derivative. (Process also claimed.) Glycocol amids. 

ACETANILID is digested 12-24 hours at 50-60° in 25-30 parts strong alc. NH,, solvent re- 
covered and residue in aq. soln. with excess NH, gives cryst. glycocol anilid. Halogen comps. 


of acetanilid, etc., and substituted ammonias, such as DIMETHYL amin, glycocolethers and amids, 
or acetyl toluidin, anisidin and phenetidin derivs., etc., may be employed. 


543,579—July 30, 1895. Leonhard Lreprerer, Germany. 
Process of producing phenoxacetic anilids, &c. Phen oxal acet 4-phenetidid and re- 
lated comps. 


Phen oxal acetic acid and 4-PHENETIDIN in equimols. are heated at 120-140° until no more 
aq. is given off. Residue is cryst. from boiling alc. List of comps. (21) with properties is given. 


563,116—June 30, 1896. Josef ZiecLteR, Germany. (Fritzsche.) 
Process of making quinolin compounds. 2-Oxy quinolin pyrosulfate, K salt, an anti- 
septic comp. 
2-Oxy QUINOLIN dissolved in 5-6 parts boiling alc. is refluxed with 1 mol. pulv. K,S,O, 
(pyrosulfate) for 10-12 hours. 


563,993—July 14, 1896. Gustav A. WELTER, Germany. (Kuchler.) 
Amidoalkylsalicylic acid. (Process also claimed.) 5-Amino and acetyl 5-amino salicylic 
acid. 


Ethyl saticyiic acid is treated with HNO, (1.2), or preferably with mixed acids, to form 
s-nitro SALICYLIc acid which is separated and digested at roo° with HCl and Sn until dissolved, 
evapd. to dryness, Sn removed from aq. soln. of residue and evapd. to crystn. The acetyl deriv. 
results when glac. acetic acid and Sn are used for reduction. 


567,968—Sept. 22, 1896. Arthur E1rcHencrttn, Germany 
lodoform combination with hexamethylenetetramine. Cryst. inodorous surgical 
compound which decomp. to give free CHI,. 
HEXAMETHYLENEAMIN is heated at roo° with equimol. CHI, in abs. alc. Phenol, chloral, alkyl 
iodide or other derivs. of hexamethylene tetramin in alc., chloroform or amyl acetate solns. may 
be employed. 


569,416—Oct. 13, 1806. Oscar Hinsserc, Switzerland. (Hochst.) 
Ester of alkoylaminophenols and method of making same. Acetyl! ethyl 4-amino 
phenyl ethyl carbonate, etc. 
Acetyl ethyl 4-amino PHENOL dissolved in calculated quantity of NaOH is treated with 
slight excess ETHYL chlor carbonate, shaken well and cooled until reaction is complete. Other i 
alkoyl amino phenyl carbonic esters are claimed. 


579,412—Mar. 23, 1897. Friedrich Stoiz, Germany. (Hochst.) 
Pyrazolon compound and process of making same. Phenyl 2.3-dimethyl dimethyl 
4-amino pyrazolone, m.p. 107—108°. 
Phenyl 2.3-dimethyl 4-amino PYRAZOLONE is heated at 90° with equal parts alcohol and 2 
mols. METHYL iodide for 1 hour; alc. distilled off and product extracted from its alk. soln. with 
benzene. Product is white cryst. comp. sol. in usual solvents except ligroin. 


<e 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 451 


596,797—Jan. 4, 1808. Ernst Tauser, Germany. (Hochst.) 


Process of making amidins. (Product also claimed.) Ethenyl 4.4’-diethoxy diphenyl 
amidin, isomers and derivs. 


PHENACETIN in benzene soln. is mixed with PCl, or other dehyd. agent, 4-PHENETIDIN in 
benzene soln. added and mixture heated several hours. Benzene is distilled off and base in aq. 
soln. of residue pptd. by NH,. 


598,914—Feb. 15, 1808. Ernst H. C. Diirxopr, Germany. (Merck.) 
Formaldehyde tannin. (Process also claimed.) Methylene ditannins. 


TANNIN and o.5 mol. FORMALDEHYDE are condensed in HCl soln. Other condensing agents 
and any form of tannic acid may be used. 


601,072—Mar. 22, 1898. Ernst H. C. Diirxorpr, Germany. (Merck.) 
Formaldehyde proteids containing iodim. (Process also claimed.) 
FORMALDEHYDE and CASEIN are condensed in HCl soln. and product suspended in aq. con- 


taining Kl and I. Or casein is dissolved in dil. (0.6 per cent) NaOH, formaldehyde added then 
soln. of Kl and I with or without HCl. Other proteids are claimed. 


602,109—Apr. 12, 1898. Israel Roos, Germany. 
Process of making salts of paramidophenol. (Product also claimed.) Citrates of 
4-phenetidin, 4-anisidin or other esters of 4-amino phenol. 


Equimols. of citric acid and 4-PHENETIDIN are brought together in alc. soln. 


602,690—Apr. 19, 1808. 
Carl Friepericu, Maria ScHAERGES and Paul ScHwarz, Switzerland. (Hoffmann.) 
Process of making alkaline acetosulfanilate. 
SULFANILIC acid, Na salt, and equal parts glac. acetic acid are refluxed 6-8 hours, excess 


acetic distilled off, residue dissolved in 0.5 parts hot aq., free sulfanilic acid filt. out and soln. 
treated with alc., which retains sod. acetate and ppts. alk. salt of aceto sulfanilic acid. 


602,690—Apr. 19, 1918. 
Carl Friepericu, Maria ScHaAgrces and Paul ScHwarz, Switzerland. (Hoffmann.) 
Acetyl derivative of phenetidinm. (Process also claimed.) Phenetidin sulfo acid and 
its acetyl deriv. 

PHENETIDIN is slowly added to 2-3 parts fuming H,SO, (10 per cent SO,) and heated at 
100-120°. Resulting phenetidin sulfo acid is converted to its Na salt and with equal parts glac. 
acetic containing some anhydride, is refluxed several hours. Excess acid is distilled off, a limited 
amount of aq. added, filt., and soln. pptd. by alcohol. 


603,195—Apr. 26, 1808. Wilhelm Mayert, Germany. 
Process of purifying orthotoluenesulfo-chlorid. Separating orthotoluene sulfo 
chloride from para comp. 

Crude To.vENE sulfo chloride containing about 70 per cent ortho and 30 per cent para comp. 
is distilled in vacuum until 30-40 per cent has distilled over. This is almost c.p. ortho deriv. 
Residue is cooled and about 10-12 per cent para deriv. crysts out. This is separated and liquid 
again distilled in part, cooled, crystd. and process repeated. 


604,503—May 24, 1808. Bruno R. Serrert, Germany. (von Heyden.) 
Process of making orthosulfamin-benzoic-acid alkyl esters. 

2-Sulfamin BENzorc acid and 0.2 parts H,SO, are dissolved in 4 parts alcohol (98 per cent), 
refluxed several hours, alc. distilled off and residue poured into cold aq. to cryst. Instead of 
H,SO, other dehydrating material may be used, and other alcohols as solvents. 


607,172—July 12, 1808. Karl Hocx, Germany. (Elberfeld.) 
Pharmaceutical compound and process of making same. Insoluble, tasteless and 
odorless tannin compound. 
Hexamethylene tetramin and 3 mols. TANNIN are mixed in cold aq. soln., ppt. filt. off, dried, 
powd., and heated at 90-100° for 30-60 mins. Or the conc. aq. soln. may be heated, or its soln. 
in glycerin heated at 110°, etc. 


452 DIGEST OF PATENTS 


610,348—Sept. 6, 1808. Alfred Ernnorn, Germany. (Héchst.) 
Esters of paraimidometaoxybenzoie acid. (Process also claimed.) Esters of 4- 
amino 3-oxy benzoic acid (m.p. 120-122°), used as ointment for wounds. 


4-Nitro 3-oxy BENZoIc acid is reduced to amino deriv. which is boiled in 4 parts METHYL 
alcohol with equal parts conc. sulf. acid, pptd. as HCl salt, purified, etc. 


615,828—Dec. 13, 1808. Henry C. Frurziin. Missouri. 
Process of purifying acetanilid. 


Anilin oil is first removed from the crude mixture with ACETANILID by a current of super- 
heated vapors of acetic acid at 180° then distillation is continued preferably under diminished 
pressure at b.p. of acetanilid while a current of superheated vapors of acetic acid at same temp. 
is again passed so that active distillation of acetanilid is effected. 


615,829—Dec. 13, 1808. Henry C. FEHRiIN. Missouri. 
Process of making acetanilid. Acetanilid made with com’]. acetic acid. 


ANILIN oil is heated to 160° and current of superheated vapors of com/’l. acetic acid at 
185° is passed through. The apparatus is equipped with a dephlegmator so that ag. vapors 
escape while acetic acid and anilin that vaporize are returned to the retort. 


618,167—Jan. 24, 1809. Alexander CiassEN, Germany. 
Sodium salt of iodin compound. Tetra iodo phenolphthalein, Na salt. 


PHENOLPHTHALEIN, 3 parts in 10 parts 40 per cent NaOH, is mixed with soln. of 10 parts 
iodin and 12 parts KI in 4o parts aq. below 20°. Red soln. becomes deep blue and is then 
cooled and cooled HCl added. The yellow brown product contains 1 mol. aq. which is lost on 
heating to 100° and the white tetraiodo phenolphthalein is produced. Reaction with iodin can 
be made by electrolysis of KI. 


618,168—Jan. 24, 1809. Alexander CiLassEN, Germany. 


Iodin derivatives of phenols and bismuth salts thereof. (Process also claimed.) 
Tetra iodo phenolphthalein and heavy metal salts. 
Tetra iodo PHENOLPHTHALEIN is produced as in 618,167 and sodium salt transposed in aq. or 
salt soln. with chlorides or other soluable salts of heavy metals such as Al, Fe, Zn, Pb, Mn, Bi, 
and Hg. 


619,549—Feb. 4, 1899. Alfred E1inyorn, Germany. (Hochst.) 
Glycocol esters and process of making same. Aromatic glycocol amino carbonic acid 
esters. 


4-Amino SALICYLIc acid, methyl ester, in benzene soln. is heated with equimol. chlor acETYL 
chloride until HCl no longer escapes and resulting cryst. chlor acetyl 4-amino salicylic acid, 
methyl ester, is refluxed with DIETHYLAMIN in alc. soln. for 2 hours and alc. evapd., leaving an 
oily residue of methyl ester of diethyl glycocol 4-amino salicylic acid. 


fA 


PE es BE Ty ai 


621,319—Mar. 21, 1899. Julius Brept, Germany. (Elberfeld.) 


Bromin derivative of phthalimid and process of making same. 
PHTHALIMID is dissolved in dil. NaOH and added to ice cold mixture of 1 mol. Br. in aq. 


P— 


624,772—May 9, 1809. Alfred E1nuorn, Germany. (Hoéchst.) 


Glycocol phenyl ester and process of making same. Glycocol phenol esters, useful 
as antiseptics. : 
CHLOR ACETIC acid is condensed with GuaracoL ester or other phenol ester to form a halogen 
acetic acid phenol ester, which is mixed and condensed with DIETHYL amin or other secondary 
amin, separated, purified, etc. 


se en 


625,158—May 16, 1899. Alfred E1nnorn, Germany. (Hochst.) 


Esters of para-oxy-meta-amidobenzoie acid and process of making same. 
4-Oxy 3-amino BENzoICc acid HCl salt, derived from nitro comp. by reduction with Sn and 
HCl, is added to 5 parts ethyl or methyl alc. and satd. with HCl, then heated at 100°. 


625,159—May 16, 1899. Alfred Ernyorn, Germany. (Hochst.) 


Glyeocolamidocinnamic-acid ester and process of making same. 
3-Amino CINNAMIC acid, methyl ester, is condensed with chlor acrtyt, chloride to form chlor 
acetyl 3-amino cinnamic acid ester, then condensed with DIETHYL amin. 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 453 


658,747—Oct. 2, 1900. Julius ALtscHuLt, Germany. (Berlin.) 
Compound of gelatin and tannin and process of making same. Gelatin tannate 


of 45 per cent tannin, not decomp. at 100-130°. 
Soln. of TANNICc acid (5 per cent) is mixed with 1 per cent soln. of gelatin, ppt. filt., pressed, 


ground, spread in thin layers to dry at 20-25° until a sample will not melt at 100°. Mass is 
then ground to powd. and dried at 100°, and if desired can be sterilized at 105-110°. 


659,204—Oct. 9, 1900. Heinrich Brat, Germany. (Berlin.) 
Bromo-tannin-zgelatin compound. 


TANNIc acid and equal parts Br are mixed in alc. soln. and, after color is lost, water is 
added then aq. 1.5 per cent GELATIN until all is pptd., washed, dried at low temp. and pulv. 


667,388—Feb. rgor. Emil Fiscuer, Germany. (Boehringer.) 


Trimethyl-pseudo-urie acid and process of preparing same. Trimethyl uric 
acid or hydroxy caffein. 


ps-uRIc acid or dimethyl or gamma methyl deriv., etc., is boiled in 500 parts 20 per cent 
HCl until dissolved then evapd. to about 35 cc., which ppts. uric acid as crysts. in about 80 per 
cent yield. METHYL amin, 33 per cent soln., is sat. with SO, then more amin added until odor 
is apparent, neut. with CO,, equal parts dimethyl ALLOXAN and ag. added, heated at 60-70° for 
1 hour and cooled to cryst. 1.3.7.-trimethyl URAMIL. When heated with KCNO this forms ps- 
1.3.7.-trimethyl uric acid and this when heated at 100° with dil. HCl finally yields 1.3.7-tri- 
methyl uric acid or hydroxy CAFFEIN. 


671,185—Apr. 2, 1901. Ludwig O. Hetmers, Germany. (Cordes.) 
Sulfonic acid salt and process of making same. Ichthyol sulfo acids as permanent 
soluble metal salts. 


Sulfo acids of sulfonated mineral oils that are not pptd. by alk. earth and heavy metal 
salts are recovered from soln. by heating with com’! H,O, evap’d and residue converted to silver 
salt, etc. Or original sulfonating soln. before pptn. by alk. earth, etc., may be oxidized by CrO,, 
etc., freed from alk. earth and silver salt formed. 

“Seefeld”? mineral oil used. 


674,686—May 21, 1901. Baptist Reuter, Germany, (Hochst.) 
Acid camphorate of phenyldimethylpyrazolon and process of making same. 


Phenyl dimethyl pyrRAZOLONE and equimol. cAMPHoRIC acid are combined as shown in 674,687. 


674,687—May 21, 1901. Baptist Reuter, Germany. (Héchst.) 
Neutral camphorate of phenyldimethylpyrazolon and process of making 
same. 


Two mols. phenyl dimethyl pyrazoLoneE, finely pulv. and dried, are mixed in ball mill with 1 
mol. pulvy. and dried campnoric acid and heated at 100°. Cooled solid mass is ground, ex- 
tracted with a little ligroin and dried at 40° in vacuum. Combination may be made in benzene 
soln. 

Note 674,686. 


676,859—June 25, 1901. Fritz Acu, Germany. (Boehringer.) 
Amido-tartroniec acid and process of making same. 

Anilin aLLoxaNn is added to boiling KOH (10 N), NH, being evolved, and soln. is then 
evapd. to crystn. of di-potassium salt of 4-amino phenyl TartRonic acid, which is dissolved in 
‘aq., boiled to remove NH, and pptd. by excess alc. acetic acid as acid salt. Free acid is ob- 
tained by converting to normal salt with KOH, filtg. through charcoal to purify and adding HCl. 
Homologs and derivs. are claimed. 


678,070—July 9, 1910. Hermann Vietu, Germany. (Knoll.) 
Biacetate of anthrapurpurin and process of making same.  bBiacetate of 1.2.7.- 
trioxy anthraquinone. 

Equal parts of ANTHRAPURPURIN and acETic anhyd. are boiled for 2-3 hours, or mixtures of 
CH,COCI or PCI, and acetic acid may be used for acetylization, preventing formation of insol. 
Binenty! deriv. By diln., by lowering of temp. or by use of only calculated quant. for the bi- 
substitute. 


454 DIGEST OF PATENTS 


680,278—Aug. 13, 1901. Baptist Reuter, Germany. (Hochst.) 
Salicylate of dimethyl-amido-phenyl-dimethyl-pyrazolone and process of 
making same. 
SALICYLIC acid and dimethyl 4’-amino phenyl 2.3-dimethyl pyRAzoLone in mol. proportions are 
heated at 100°, dry or in boiling alc. soln. 


686,998—Nov. 19, 1901. b Alfred AmMELBuRG, Germany. (Hochst.) 
Neutral compound of dimethylamidodimethylphenylpyrazolon and process 
of making same. 


Dimethyl amino dimethyl phenyl PyrazoLonE, 2 mols., is mixed with 1 mol. anhyd cam- 
PHORIC acid in dry ether soln. then condensed in vacuum without access of light. ‘The ether is 
dried with Na and reaction must take place in absence of moisture, light and heat. Product is 


white powd. m. p. 81-2°. 
Note 674,686-7. 


686,999—WNov. 19, 1901. Alfred AmmeE.sure, Germany. (Hochst.) 
Acid compound of dimethylamidodimethylphenylpyrazolon and process of 
making same. 


Process is similar to 686,998 using equimols of dimethyl amino dimethyl phenyl PyRAZOLONE 
and CAMPHORIC acid. 


690,804—Jan. 7, 1902. George Wicumann and Max GaBLER, Germany. (Chem. Fab.) 
Salt of hexamethylentetramin and quinie acid and process of making same. 


Molecular quantities of QUINIC acid and HEXAMETHYLENE tetramin are mixed in alc. soln. 
which is filt. and evapd. in vacuum. Salt contains about 58 per cent of acid and 42 per cent 


of amino compound. 


709,321—Sept. 16, 1902. Ludwig O. Hetmers, Germany. (Cordes.) 
Process of separating sulfonic acids. 

IcutHyot sulfo acid, or other mixed sulfo deriv., may be separated into its higher and 
lower sulfonated components by combining with ANILIN, PIPERAZIN or different organic bases 
which form compounds of varying solubilities with the different sulfo derivs. 

Note 671,135. 


- 


710,005—Sept. 30, 1902. Ralph H. Pacer. Michigan. 


Process of making organic peroxide. Benzoyl acetyl peroxide, etc. 

BENZALDEHYDE or other aromatic aldehyde, is mixed with equal parts acETIC anhyd. and 
oxidized by air, or other agent,-in film form, that is in thin layers on plates or disks or on 
sheets of absorbent material such as muslin or unsized paper. Apparatus is shown and process 
described. Oxidation is so restricted that peroxide is formed in excess of benzoic and acetic 


acids as by-products. . 


717,016—Dec. 30, 1902. Ralph H. Pacer, Michigan. 
Organic peroxide. Acetyl hydrogen peroxide. 

BENZOYL acetyl peroxide derived as in 710,005 in aq. soln. splits up forming a ppt. of y, 
DIBENZOYL peroxide, in soln. of acetic acid and acetyl hydrogen peroxide. The filt. soln. con- 
tains comp. claimed by patent, which has not as yet been successfully separated from accom- a 
panying acetic acid. = 

# 
741,585—Oct. 13, 1903. Oscar Liesreicn, Germany. 


and the product thereof. (Process only claimed.) 

A fat such as ox tallow is heated with an excess (more than 3 mols.) of ANILIN at 200° 
for 12-24 hours. Resulting anhyd. glycerin and anilid or aromatic amid of fatty acid are sep- a 
arated by crystn. or frac. distn. at low pressure. Anilin in excess distils at 60-65°, then anhyd. a 
glycerin at 170° and anilids at 300-360°. Mixtures that produce aromatic bases can be used, 


such as anilin HCl and CaO. 


Process of producing glycerin and acidylated derivatives of aromatic bases © e 
a 
4 


748,101—Dec. 29, 1903. Eduard RitsEert, Germany. 


Aromatie esters and process of making same. 
Two mols. 4-amino BENzoIc acid, ethyl ester, or isomers, are dissolved in hot aq. soln. of 
1 mol. BENZENE 3-disulfo acid. On cooling the ester separates and by concn. a further crop of 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 455 


crysts. is obtained. Salts of above comps. may be used and instead of disulfo benzene ortho or 
para phenol sulfo acids and esters. 


749,634—Jan. 12, 1904. Bruno R. Srirert, Germany. (von Heyden.) 
Acetyl para cresotinie acid. A substitute for acetyl salicylic and with less action on 
heart. 


Two parts 4-CRESOTINIC acid and 3-4 parts acetic anhyd. are refluxed. Reaction can take 
place in solvents like benzene, CCl,, etc., acetyl chloride may be used and also an agent to 
hasten condensation, such as H,SO,, pyridin, other bases, etc. 


768,398—Aug. 23, 1904. Martin Ovrertacu, Germany. (Héchst.) 
Pyrazolone compound and process of making same. 


Butyy chloral hydrate is melted at 100° with 1 mol. dimethyl 4’-amino phenyl 2,3-dimethyl 
PYRAZOLONE. Condensation may take place in aq. or benzene soln. 


768,562—Aug. 23, 1904. Alphonso M. Crover, Michigan. 
Process of forming organic peroxid acids.  Succinic peroxide acid. 


Succinic anhyd. is pulverized and mixed with 17 per cent H,O, soln., stirred 35 minutes, 
product filt. and dried in vacuum. 


773,251—Oct. 25, 1904. Emil Fiscuer and Josef Mrrtnc, Germany. (Merck.) 


Ureide of dialkyl-acetic acid and process of making same. Diethyl acetyl urea 
or the dimethyl, dipropyl or mixed alkyl derivs. 


Diethyl Matonic acid is mixed with equal parts uREA and POCI, added. When action has 
ceased heat is applied (100°) for several hours, mass extracted with a little aq. and residue re- 
cryst. Reaction can take place in two stages, first eliminating H,O with fuming H,SO, (40 
per cent SO,) and heating separated product to 162° to remove CO,,. 


801,158—Oct. 3, 1905. Rudolf Reiss and Otto ScuMarotia, Germany. 
Process of making insoluble aluminum acetate. 


A 15 per cent soln. of Al acetate is mixed with 0.33 vol. of conc. AcETIC acid and stirred 
while boiling until pptn. ceases. Or soln. may stand some time or be heated in an autoclave. 


811,884—Feb. 6, 1906. Friedrich W. S. VALENTINER, Germany. 
Salicylic-acid methylene acetate and process of making same. 


Acetyl saticyLic acid, m.p. 135°, free from salicylic and acetic acids, is mixed with 1 mol. 
FORMALDEHYDE (40 per cent) and heated on sand bath till dissolved, cooled, ground and re- 
cryst. from aq. 


812,554—Feb. 13, 1906. Alfred Ernuorn, Germany. (Hochst.) 
Alkamin esters of para-aminobenzoie acid. 


4-Nitro BENZOyL, diethyl amino ethanol (obtained by heating ETHYLENE chlorhydrin with 
4 nitro BENzOYL chloride and the resulting 4-nitro BENZoyL ethanol heated at 100—-120° with ro 
parts DIETHYL amin) is digested at moderate temp. with 1.3 parts Sn and 2.5 parts conc. HCl. 
Tin is removed by H,S and product pptd. with Na,Co,. Other alkamin esters are claimed. 


812,608—Feb. 18, 1906. Alfred StepHAN, Germany. 


Process of making a formic-aldehyde compound. 

PHENOL is heated in autoclave at 100° with 0.5 parts 40° KOH and 2 parts CH,O. After 
first reaction ceases comp. is heated at 100° until the dild. sample ppts. with acid. The alkali 
acts as a condensing, polymerizing and solvent medium. 
8$21,291—May 22, 1906. Alexis C. Houcuton, New York. 
Benzoyl succinyl peroxid and process of making same. (Process not claimed.) 

Succinic anhyd. is added to 2 parts BENzoIC peracid in 10 parts aq. Product separates as 
fine powd. 
830,043—Sept. 4, 1906. Bertrand Bisus and Rudolf ScuEusiEe, Austria Hungary. 
Process for producing salicylic-acid-menthol ether. 


MENTHOL and 4.7 parts SALICYLIC acid (1 mol. each) are heated at 140-220° on oil bath and 
dry gas such as H, CO, or HCl at same temp. is blown through mixture to remove H,O formed. 


456 DIGEST OF PATENTS 


Mixture is diluted with an organic solvent, neut. with Na,CO, and fractionated. By-products 
are recovered as shown in patent. 


837,083—Nov. 27, 1906. Otto LirBKNEcut, Germany. (Roessler-Hass.) 
Process for the manufacture of glycolic acid. Glycolic acid by electrolysis. 


Cryst. oxaLic acid dissolved in 4.5 parts aq. and 1.5 parts 30 per cent H,SO, form the 
cathode liquor and 30 per cent H,SO, the anode liquor. Electrodes must be of high cathode 
over voltage, such as is given by lead, with a current of 25-250 amps. per sq. meter of cathode 
and a diaphragm to limit anodic oxidation. Not less than 15 per cent H,SO, or 20 per cent 
HCl is-recommended. After electrolysis these are removed in usual ways. 


852,993—May 7, 1907. Peter BrercreLtt, Germany. (Wilfing.) 
Hexamethylenetetramin-sodium acetate double salt. (Process also claimed.) 


One mol. HEXAMETHYLENE tetramin and 2 mols. sod. acetate 6 aq. are evap’d. to crystn. in 
vacuum. 


854,452—May 21, 1907. Henry S. BLackmore, New York. 
Formaldehyde preparation. (Process also claimed.) Oxy acid esters as solvents of 
formaldehyde to obviate pungent odor as disinfectant. 


BENzotc acid ethyl ester, or other oxyacid ester, and FORMALDEHYDE are subjected to super 
atmospheric pressure until absorbed. Solns. up to 80 per cent formaldehyde can be made. An 
inert diluent may be used, such as camphor oil. 


869,636—Oct. 29, 1907. O. Manxrewicz, J. ALTscHUL, and W. Ursan, Germany. (Berlin.) 
Borate of hexamethyleneamin and process of making same. 


Boric acid and 2.25 parts HEXAMETHYLENE amin are ground together and mass dried at 
60-70°. Product contains 33 per cent boric acid and 30 per cent N. Other proportions may 
be used and reaction takes place dry or in aq. or alc. soln. 


$86,085—Apr. 28, 1908. Gerhard StaunMann, Germany. (Schimmel.) 
Process of manufacturing protocatechuie aldehyde. 


PIPERONAL is heated at 130° with nearly 2 parts protochloride of sulfur, $,Cl,, until HCl 
has all escaped, then boiled with aq. for 8 hours till CO, has also been removed. Sulfur is 
filt. out and protocatechuic aldehyde extracted by ether. Sulfuryl chloride or sulfur and Cl 
can be used, and piperonyl chloride with sulfur dichloride, SCl,. 


889,171—May 26, 1908. Henry S. Brackmoret, New York. 
Formic-aldehyde preparation and process of making same. 


Claims are similar to 854,452 but are more specific for the methyl esters of oxy SALICYLIC 
acid. 


906,918—Dec. 15, 1908. Leopold Ostermann, Germany. 
Process of making neutral oxychinolin salts. 

Oxy guinotin and H,SO, (65.5°) are mixed in 96 per cent alc. soln., crysts. filter pressed 
and dried at 55-60°. Two mols. H,SO, are taken up. In aq. soln. one of these splits off. 
Recrystn. can be made from alc. soln. 


922,995—May 25, 1909. L. Acu and T. Surrer, Germany. (Boehringer.) 
Salicylic-acid derivative and process of making the same. Salicylic acid 
anhydride or salicyl-salicylic acid. 

SaLicyiic acid is dissolved in 1.5 parts of mixture of dimethyl anizrw and benzene (4:1) 
and o.2 parts POCI, in benzene soln. introduced by drops, with stirring and cooling, let stand 
several days and added to excess 12 per cent HCl. Liquid is siphoned from crysts. which 
are boiled with aq. to remove unchanged salicylic acid. Modifications of process are given. 
Condensing agent is used in quantity to split off 1 mol. only of aq. from 2 mols. acid. 


936,380—Oct. 12, 1909. F. Stotz and K. Srrerrwoir, Germany. (Hochst.) 
1-Para-dialkylamino-2.4-dialkyl-3s-oxymethyl-5-pyrazolone. 


4-Amino phenyl 2.4-dimethyl 3-oxy methyl PYRAZOLONE, 5 parts, is heated at 90-100° with 
3 parts METHYL iodide and 4 parts METHYL alc. for 6 hrs. Alcohol is distilled off and product 
extracted by CHCl, from soln. after satn. with NaOH. 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 457 


942,674—Dec. 7, 1909. Hans ScHNEIDER, Germany. 
Method of making diphenyl-ortho-oxalic esters. 
Two parts liq. pure PHENOL at 40° are poured over 1 part anhyd. oxauic acid. When mix- 


ture thickens temp. rises from 30° to nearly 100° and a dry mass of phenol oxalic acid ester 
results. Trade name is “Phenostal.’’ 


948,084—Feb. 1, 1910. Lorenz Acu, Germany. (Boehringer.) 


Esters of diglycollic acid and preparation of same. Guaiacol ester of diglycollic 
acid, or other. 


A dihalogen comp. of DIGLycotic acid is caused to react with a PHENOL in presence of halo- 
gen hydride binding agent. 


950,936—Mar. 1, 1910. Richard Lupers, Germany. 
Process of making the n-propyl ester of p-aminobenzoic acid. (Product also 
claimed.) 


4-Nitro BENzoIc acid is boiled in 5 parts N-propyt alcohol with 1 part H,SO, or other water 
absorbing agent. Excess alc. is removed, acid neut. by Na,CO,, or other, and insol. ester sepd. 
and reduced by boiling in 3 parts HCl with 1 part Sn, then product pptd. by Na,CO,, etc. 


966,820—Aug. 9, 1910. Albert FrigpLAENDER, Germany. (Horowitz.) 
Process of rendering hydroxyl derivatives of aromatic hydrocarbons soluble 
in water. 
A mixture of cresols or 4-CRESOL, ALIZARIN, or other insol. hydroxy deriv. of aromatic 
hydrocarbons is rendered soluble by mixing with RESORCIN, PHENOL, pyrocatechin, etc. Materials 
may be mixed dry in tablets for hygienic or cosmetic purposes. 


990,310—Apr. 25, 1911. F. Stoiz and G. KornporFer, Germany. (Hochst.) 
1-Para dimethylaminophenyl 2.3.4-trimethyl 5-pyrazolone and process of 
making same. 
4'-Amino phenyl 2.3.4-trimethyl PYRAZOLONE is heated with 0.5 parts METHYL iodide and 0.5 
parts METHYL alc. at go-100° for 5 hours, cooled, dissolved in aq., sat. with alk. and extracted 
with benzene, or other. Or 4’-nitro phenyl 2.3.4-trimethyl PYRAZOLONE of 936,380 can be re- 
duced with Sn and HCl. 


998,726—July 25, 1911. Hermann Vietu, Germany. (Knoll.) 
Phenolphthalein diisovalerate. (Process also claimed.) 


PHENOLPHTHALEIN is heated at 100° with 1.2 parts ISOVALERYL bromide until HBr no longer 
escapes, mass is dissolved in benzene and shaken out with dil. NaOH. 


1,017,699—Feb. 20, 1912. ; Friedrich Stouz, Germany. (Hochst.) 
1-p-Dimethylaminophenyl1-3.4.4-trimethyl-5-pyrazolone and process of 
making same. 

Phenyl 3.4.4-trimethyl PYRAZOLONE is dissolved at 10-20° in 7 parts conc. H,SO, and 1.25 
parts mixed acid (26 per cent HNO,) added drop by drop at o-5°. The 4’-nitro phenyl deriv. 
is separated and poured into 4 parts conc. HCl and 1.15 parts Sn slowly added. Tin is re- 
moved by H,S, pyrazolone base pptd. by NaOH and heated to go-100° for 6-8 hours with 0.7 
parts METHYL iodide and 0.5 parts METHYL alcohol. 


1,028,074—May 28, 1912. Leopold Kauxt, Germany. (Rutgers.) 
Ortho-oxalic-acid ester of meta-cresol and process for the manufacture of 
the same. 
Two mols. 3-cRESOL are ground with 1 mol. anhyd. oxaric acid at 15-20° and let stand until 
dry powd. forms. 


1,036,087—Aug. 20, 1912. Paul FLEMMING, Germany. 
Halogenphenolalkali salts and process for the manufacture of same. 


4-Chlor 3-crEsoL or other halogen phenol, in benzene or other organic solvent is treated 
with KOH or other alkali. 


458 | DIGEST OF PATENTS 


1,045,377—Nov. 26, 1912. Max Dourn, Germany. (Chem. Fab.) 
Methyl ester of 8-methoxy-2-phenylquinolin-4-carboxylic acid. 


Dry HCl gas is passed some hours through a METHYL alc. soln. of 8-methoxy 2-phenyl 
QUINOLIN 4-carbo acid, pptd. with aq. and extracted by ether. 
Note 1,045,378. 


1,045,378—Nov. 26, 1912. Max Donrn, Germany. (Chem. Fab.) 
Ethyl ester of 8-methoxy-2-phenylquinolin-4-carboxylic acid. 


Process is similar to that of 1,045,377, using an ETHYL alc. soln. 


1,045,379—Nov. 26, 1912. Max Dourn, Germany. (Chem. Fab.) 
Methyl ester of 6-methyl-2-phenylquinolin-4-carboxylic acid. 


Process is similar to that of 1,045,377 using 6-methyl 2-phenyl QUINOLIN 4-carbo acid instead 
of the 8-methyl] deriv. 


1,045,759—Nov. 26, 1912. Albrecht THIELE, Germany. (Chem. Fab.) 
Ethyl ester of 6-methylI-2-phenylquinolin-4-carboxylie acid. 


Process is similar to that of 1,045,379, using ETHYL alcohol. 


1,053,240—Feb. 18, 1913. Friedrich Stoiz, Germany. (Hoéchst.) 
Pyrazolone derivative. 4/-Brom PHENYL 2.3-dimethyl 4-iodo pyrazolone. 
One mol. powd. iodin is introduced while stirring into a benzene soln. of 1 mol. 4’-brom 


phenyl 2.3-dimethyl PyrRAzoLONE and heated 2 hours at 50-60° then aq. soln. of Na,CO, (14 
per cent) in excess added and mixture refluxed. Product is recovered from the benzene soln. 


1,053,300—Feb. 18, 1913. G. KornporFer and B. Reuter, Germany. (Hochst.) 
Derivatives of diaminodioxyarsenobenzene and process of making same. 
Formaldehyde sulfoxylate deriv. of diamino dioxy arseno benzene. 
Diamino dioxy arseno BENZENE 2HCI in 10 parts aq. is slowly mixed with 0.5 parts FoR- 


MALDEHYDE sulfoxylate in 5 parts aq. After 1 hour 3.2 parts 10 per cent Na,CO, are added to 
form Na salt of the mono or dimethylene sulfinic acid diamino dioxy arseno benzene. 


1,056,881—Mar. 25, 1913. M. Bockmuny and G. Esrert, Germany. (Hochst.) 
Alkylsulfites of amino-substituted pyrazolones and process of making same. 

Formaldehyde sulfoxylate comp. of 4-antipyrylamin. 

Phenyl 2.3-dimethyl 4-amino PYRAZOLONE (4-antipyrylamin), 100 parts, is dissolved by warm- 
ing in 37 parts of 38 per cent FORMALDEHYDE and 132 parts (39 per cent) bisulfite in flat basins 
and let stand some days at 15-50°, then solid sepd. from liquid, extracted with 15 parts methyl 
alc., filt. and soln. evapd. in vacuum to crystn. 


1,058,904—Apr. 15, 1913. Gedeon RicutER, Austria-Hungary. 
Process for the formation of calcium salt of acetylsalicylic acid. 

Acetyl saLicyLic acid is mixed with 2 parts aq. then 0.35 parts CaCO,, added gradually with 
stirring. When no more CO, escapes mixture is quickly filt. and 3-4 parts alc. added to ppt. 
Ca salt. 


1,059,983—Apr. 29, 1913. P. Euriticu and A. BertHEeim, Germany. (Héchst.) 
Alkali compounds of dioxydiaminoarsenobenzene.  4.4’-Dioxy 3.3’-diamino arseno 
benzene, disodium salt. 


Diamino dioxy arseno BENZENE is suspended in about 10 parts methyl alc. and without 
access of air, 2.6 parts 5 per cent METHYL alc., Na salt, are mixed and stirred till dissolved, filt. 
in H or N atmosphere, run into abs. alc., filt., etc., and dried in vacuum. Entire process is 


carried out in absence of oxygen. 


1,060,765—May 6, 1913. Ludwig Kaufmann, Germany. 
Organic antimony compounds and process of making same. Triphenyl stibine 
sulfide, homologs, and derivs. 

TRIPHENYL stibine dibromide, or other haloid deriv., is dissolved at common temp. in 16 
parts sat. alc.-NH, soln., (from 99 per cent alc.), filt., and uniform current of purified H,S 
introduced with stirring until pale yellow color just disappears by violent shaking, crysts. dried 
by suction, washed with alc., etc. Yield is 80 per cent. 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 459 


1,063,099—May 27, 1913. Richard WoLFFENSTEIN, Germany. 
Acidylsalicyliec acid ester and process of making same, 


Acetyl sALicyLic acid chloride is mixed with 0.8 parts QUINOLIN with cooling then 0.4 parts 
abs. alc. added, heated 30 m. at 100°, ligroin added and shaken with dil. HCl then dil. Na,CO, 
and finally aq., dried with anhyd. Na,SO,, ligroin distilled off then the ethyl ester of acetyl 
salicylic acid also distilled off. Trichlor isopropyl or isobutyl alcohol or other halogen alcohols 
with CaCO, or dimethylanilin, etc., to combine with HCl set free by reaction may also be em- 
ployed. 


1,075,581—Oct. 14, 1913. 
E. Korrtscuni and O. Fopor, (Germany.) and I. Karczac, Austria-Hungary. (Karczag.) 
Anhydrid of salicylic acid and process of preparing the same. 


SaLicyLic acid chloride is mixed with 0.5 mol. CaCO, heated at 50-70° and product ex- 
tracted with large yolume warm ag. leaving an oily mass that solidifies on cooling. Tertiary 
bases such as pyridin or diethylanilin remove the HCl more smoothly than CaCQ,. 


1,076,160—Oct. 21, 1913. Rudolf Scuwasr, Germany. (Hochst.) 
Hexamethylenetetramin salts of the a-phenylquinolin-y-carboxyliec acids. 
One mol. HEXAMETHYLENE tetramin is boiled in 15 parts abs. alc., 1 mol. 2-phenyl QUINOLIN 


4-carbo acid added and cooled to crystn. 4-Methoxy PHENYL cinchonic acid will produce an an- 
alogous comp. 


1,076,840—Oct. 28, 1913. Heinrich REINHARDT, Germany. (Kalle.) 


Manufacture of diacidyl and higher acidylated compounds from amino-azo 
bases. (Product also claimed.) 


Amino azo TOLUENE, homolog, analog or deriv., is refluxed in 3 parts acetic anhyd. with 
addition of 0.2-0.4: parts sod. acetate until (from 4-10 hours) a sample does not cryst., on cool- 
ing. Excess of acidylating agent causes at least one more acidyl group than amino groups to 
enter new comp. 


1,086,8S81—Feb. 10, 1914. Clemens ZoLLNER, Germany. (Chem. Fab.) 
Glycolic acid esters of 2-phenylquinolin-4-carboxylic acid. (Process also 
claimed.) 


2-Phenyl QUINOLIN 4-carbo acid and equimol chlor acrTic acid, ethyl ester, are heated at 
120° in alc. under pressure. Filtrate, sepd. from NaCl, is fractionated in vacuum, the alc. and 
excess ester passing over first then above 250° and 15 mm. the 2-phenyl quinolin 4-carbo glycolic 
acid ester is distilled as clear yellow oil of aromatic odor. 


1,087,157—Feb. 17, 1914. P. Enrticu and H. Baver, Germany. (Hochst.) 
Colored compounds of the seleno-azin series and process of making same. 
2.4-Diamino phenaz selenonium hydroxide. 
Picryt chloride and 2-amino seleno PHENOL are condensed to dinitro pheno seleno azin which 
is reduced with SnCl, and HCl below 50° then cooled to separate tin salt of leuco base, tin 
removed by H.S and soln. oxidized with FeCl,. 


1,091,870—Mar. 31, 1914. Albrecht THIELE, Germany. (Chem.Fab.) 
Sulfo compounds of quinolin-4-carboxylic acids arylated in the 2 position. 

2-Phenyl QUINOLIN 4-carbo, acid or deriv., is heated on oil bath at 175-190° for 6-7 hours 
with 6.67 parts fuming H,SO, (1.4 per cent SO,), cooled, diluted and let stand to cryst. Or SO, 
vapors may be passed into quinolin deriv. at 40o-45°, product neut. with CaCO, and sol. Ca salt 
converted to Na comp. 


1,120,700—Dec. 15, 1914. P. Euriicu and P. Karrer, Germany. (Hochst.) 
Arseno-azo compounds and process of making same. Two mols. azo bodies united 

directly by two As-atoms. 

3-Amino 4-oxy PHENYL arsinic acid, is coupled with PHLOROCLUCIN and 2 mols. resulting azo 
comp. condensed by boiling in 35 per cent hypophosphorous acid. Other components are claimed. 
Patent refers repeatedly to products as dyestuffs, stating that H,O, will convert them into 
“starting” azo dyestuffs. | 

30 


460 DIGEST OF PATENTS 


1,138,936—May 11, 1915. Alex B. Davis. Indiana. (Eli Lilly.) 
Quinolin compounds and process of producing the same. 4/-Oxy 3’-methoxy 
2-phenyl quinolin 4-carbo acid substituted in quinolin nucleus by an organic radical. 


Equimols. of VANILLIN and 4-ToLUIDIN are boiled in abs. alc. 15 mins. and 1 mol. PYRUVIC 
acid in equal vol. abs. alc. slowly added during 30 m., then mixture boiled 3 hours, and let 
stand to cryst. Methyl group takes position 6 in quinolin ring. 


1,181,485—May 2, 1916. Rudolf ScHwasr, Germany. (Hochst.) 
Oxyphenylquinolin-dicarboxylic acid and process of making same. 


IsatIN is dissolved in 33 per cent KOH to give isatinic acid, equimol. aceto saLIcyLic acid 
added and whole heated at 100° for 8 hours, then pptd. by excess HCl. 


1,183,711—May 16, 1916. J. ALtscHuL and W. Ursan, Germany. (Berlin.) 


Compounds of the safranin dyes especially adapted for internal use. (Pro- 
cess also claimed.) 


Tolu SAFRANIN HCl, 1 mol. in ag. soln., is pptd. by 2 mols. Tannic acid, Na salt. 


1,197,462—Sept. 5, 1916. Max Dourn, Germany. (Chem. Fab.) 
2-Naphthylquinolin-4-carboxylic acids. 

IsaTin, 1 mol. in alc. soln., is heated at 100° with 1.6 parts 33 per cent KOH and o.5 parts 
a-aceto NAPHTHONE, alc. distilled off, soln. neut. with HCl and Na salt pptd. from Na,CO, soln. 
Isomer from beta naphthone is claimed: Or ANILIN is heated at 100° in alc. soln. with NAPHTHYL 
1-aldehyde and while boiling an alc. soln. of PyrorAcEMIc acid gradually added. 


1,230,185—June 19, 1917. Richard Luprrs, Germany. (Hoéchst.) 
1l-Iodo 2.3-dihydroxypropane and process of making same. 

a-CHLORHYDRIN is digested in the dark for several days at 30-35° with 1.5 parts dry, finely 
powd. Nal, then heated at 75° till all salts are pptd., filt., organic solvents distilled off, water 
added and SO, passed in to decolorize, excess SO, removed by air current and residue ex- 
tracted with ether and ethyl acetate. 


1,285,703—Nov. 26, 1918. Leo Hermanns, Germany. (Hochst.) 


Process for the production of new derivatives of the hydantoin. (Product 
also claimed.) Phenyl ethyl hydantoin and other aryl alkyl derivs. 


PHENYL cyan acetamid in abs. alc. soln. is acted upon by metallic Na in abs. alc., ethyl 
bromide added and mixture boiled on water bath. Or phenyl ethyl cyan acetamid is boiled in 
soln. of NaOBr, treated with SO,, filt., and pptd. by HCl. Other hypohalogen salts will react 
with other aryl alkyl cyan acetamids. 


1,286,944—Dec. 10, 1918. Alphonso M. Ciover, Michigan. (Parke, Davis.) 
Trimethylene glycol disalicylate and method of preparing the same. 


Trimethylene GLycon is gradually mixed with 0.5 parts conc. H,SO,, keeping temp. below 
100°; SALICYLIc acid, 2 parts, is added and mixture heated at 100° in moisture tight vessel, poured 
into a limited amount of aq. and heated to 50° to melt product, soln. neut. with Na,CO, and 
stirred to extract unchanged salicylic acid from the oily product, which solidifies on cooling. 


1,297,952—Mar. 18, 1919. John McE. Wurts, Mississippi. 
Arsenical medical product and process of producing same. Dimethyl phenyl 
hydrogen sodium arsenide. 


One part BENzoIc acid, Na salt, is ground with 2 parts sod. cacodylate, 40 parts aq. added 
to dissolve mixture, and filt. soln. evapd. dry in vacuum. 


1,299,214—Apr. 1, 19109. Karl J. Oxcusiin, France. 
Aliphatic acids containing an arSenoarylamin group. (Process .also claimed.) 
Stable comp. of formaldehyde with arseno phenyl glycin. 


Arseno PHENYL glycin in 6 per cent Na,CO, soln. is treated with an equal volume of 40 
per cent FORMALDEHYDE and pptd. by alc. or acetone. 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 401 


1,299,215—Apr. 1, 19109. Karl J. Orcusuin, France. 
Aliphatic acids containing an arsenoarylamin group. JN-Acetyl arseno phenyl 
glycin. 


Acetyl PHENYL glycin arsinic acid is warmed in 60 parts 16.67 per cent sod. hydrosulfite 
for 2 hours at 45-55°, then 1.4 parts acetic acid added. Or arseno phenyl glycin in 10 parts 
8 per cent Na,CO, is mixed at 5° with 1-1.5 parts acetic anhyd. and pptd. with excess 10 per 
cent HCl. 


1,305,462—June 3, 1919. Wilhelm Grurrerien, Germany. (Synthetic.) 
Yohimbin-earsenic pharmaceutical product. 


Arsenic acid or alphyl deriv., and yoHIMBIN are dissolved in large amount aq., filt., evap. 
and dry residue mixed with acetone, filt., and dried at 100°. 


1,306,439—June 10, 1919. Harley W. RHopDEHAMEL, Indiana. (Lilly.) 
Compounds of halogen acids with 2-phenyl quinolin 4-carboxylic acid. 
(Process also claimed.) 
2-Phenyl QUINOLIN 4-carbo acid is mixed with excess halogen acid, such as HI, and dried. 


1,306,512—June 10, 1919. Chester E. AnprEws, Pennsylvania. 
Synthetic manufacture of thymol.  1-Methyl 3-oxy 4-isopropyl benzene. 

Amino CYMENE is refluxed 15-20 hours in 1.5-2.0 parts glac. acetic and resulting acetyl amino 
CYMENE dissolved in 4.4 parts 98 per cent H,SO,, cooled to 0° and mixed acid, 1.21 parts, added 
at same temp. The 4-nitro acetyl amino cYMENE is boiled in 50 parts conc. HCl to form hydro- 
chloride, diazotized, reduced by boiling with alc. or alk. SnCl,, etc., to methyl 3-nitro 4-isopropyl 
BENZENE which is reduced with Fe and HCl, or by H and catalyzer. Amino comp. then is 
diazotized, boiled in aq. and thymol recovered by steam distn. or solvents. 


1,308,071—July 1, 1919. 
B. Htymann, O. Dresset, R. Korue, and A. OssenBEcK, Germany. (Synthetic.) 

Ureids of substituted aminonaphthol substances. (Process also claimed.) Urea 

substituted by two mols. benzoyl 1-amino 8-naphthol 4.6-disulfo or analogs. 

4-Nitro BENZoyL chloride, or analog, is condensed with 1-AMINO 8-NAPHTHOL 4.6-disulfo acid, 
or other, reduced, the neut. Na salt formed in aq. soln., sod. acetate added and PHOSGENE in- 
troduced at 40-45° until NH, group will not react with nitrite. The neutral salt is sepd. by 
usual methods. 


1,308,418—July 1, 19109. M. GuccENHEIM and E. Huc, Switzerland. (Hoffmann.) 
Process for making ethanol-trialkyl-arsonium hydroxids. 

TRIMETHYL arsin or ethyl deriv., and equimol sym. dibrom ETHANE are heated at 100° for 
3 hours and resulting arsonium condensate hydrolyzed in ro parts aq. at 180° to ethanol tri- 
methyl arsonium bromide which is taken up in alc. soln. and pptd. by ether then converted to 
hydroxide by Ag,O. Conversion of halogen alkyl into ethanol deriv. by hydrolysis with aq. 
is essential feature of claim. 


1,308,414—July 1, 1919. M. GuccenHEIM and E. Hue, Switzerland. (Hoffmann.) 
Ethanol-trialkyl-arsonium hydroxids and process of making the same. 

Process is similar to 1,308,413, using GLycor chlorhydrin or bromhydrin in place of dibrom 
ethane, whereby the ethanol deriv. is directly produced. 


1,313,657—Aug. 19, 19109. John Mc. C. Wuirte, Mississippi. 
Antisyphilitic arsenical preparation and process of making the same. 
Sodium methyl xylyl or tolyl arsine or K or Li deriv. 
Benzyz alcohol and sod. cacodylate or sod. methyl arsenide, in equimols., are mixed in aq. 
soln. at room temp. with or without NaHCO, or other mild alkali. Preparation is made just 
before sterilizing for use. 


1,315,127—Sept. 2, 1919. 
W. A. Jacoss, W. H. Brown, M. HEIDELBERGER and L. Pearce, New York. (Rockefeller.) 


Arsenical compound. Alkali salt of arseno bis=(phenyl glycocoll 3’-oxy-anilid.) 
Alkali metal salt of comp. described in 1,280,123 is formed by mixing N(4-arseno PHENYL 
glycin) bis=(3’-oxy ANILID) with 4 per cent NaOH, then concentrated at low temp. and reduced 


pressure, or pptd. by acetone. 


462 DIGEST OF PATENTS 


1,316,047—Sept. 16, 1919. Heinrich Kusxi, Switzerland. (Hoffmann.) 
Process for the manufacture of easily-soluble compounds of the C. C. 
dialkylbarbituric acids. (Product also claimed.) 


One part powd. diethyl BarBiTuRic acid is well stirred with 0.55 parts DIETHYL amin, or 
homologs of these in corresponding proportions are combined in aq. soln. 


1,317,250—Sept. 30, 19109. Ernest A. WILpMAN, Indiana. (Parke, Davis.) 


Alkamin esters of alkoxy-amino-benzoic acids and other similar compounds 
of said acids. 3-Amino anisoyl diethyl amino ethanol, etc. 


Equimols. 3-nitro ANISOYL chloride and diethyl amino ETHANOL combine when mixed together 
at usual temp. and product in 2.5 parts HCl (1.2) and 2 parts alc. is heated to 35° with 1.2 parts 
Sn. Tin salts are removed by H,S, soln. pptd. by Na,CO, and product converted to HCl salt. 
Alkoxy amino BENZOIC acids and dialkyl amino esters in general are claimed. 


1,317,251—Sept. 30, 1919. Ernest A. WiLpMAN, Indiana. (Parke, Davis.) 
Alkamin esters of amino-toluic acids and other similar compounds of said 
acids. 


Process is similar to 1,317,250 using 3-nitro 4-ToLUyL chloride for the anisoyl deriv., con- 
densing with diethyl amino ETHANOL, reducing with Sn to amino deriv. and pptg. as HCl salt. 


1,321,307—Nov. 11, 19109. Harold Hispert, New York. (Com. Research.) 
Purification of acetyl-salicylic acid. Removing impurities from acetyl salicylic acid 
by new solvent. 
Crude acetyl saLicyLic acid is dissolved in boiling dichlor olefin hydrocarbon such as C,H,Cl, 
and crystd. on cooling, the solvent retaining salicylic acid and other impurities. As solvent the 
dichlor hydrocarbons obtained by chlorinating oil gas are of particular value. 


1,330,288—Feb. 10, 1920. Umetaro Suzuk1, Japan. 
Sodium compound of dioxy-diamino-arseno-benzol-dihydrochlorid. (Processs, 
not product, claimed.) Salvarsan in form ready to use. 

Dioxy diamino arseno BENZENE, HCI salt, is moistened and dissolved in 7-9 parts methyl 
or ethyl alc. then added to 4-5 parts of a soln. of 4 g. Na in roo cc. abs. alc. Ppt. first formed is 
redissolved. (Just sufficient sod. ethylate is employed to give clear soln. when 2-3 test drops 
are added to 3-5 cc. aq., avoiding excess.) The whole is poured into a large volume of ether 
containing 0.6-1 per cent alc. to ppt. the aq. sol. product. 


1,331,712—Feb. 24, 1920. Oliver Kamm and Ernest H. VoLiweiLer, Illinois. (Abbott.) 
Di(normal) butyl barbituric acid. 

N-BuTYL bromide reacts with MALONIC ester in presence of 2 mols. sod. ethylate to give 
N-dibutyl MALONIc ester and 157 grams of this in 1 liter alcohol containing 40 g. Na are mixed 
with 50 g. UREA and heated for 6 hours in an enameled autoclave at 1o00-110°. After alc. is 
distilled off, water is added and product pptd. with HCl. 


1,332,680—Mar. 2, 1920. ; Max Pui.uips, Wisconsin. (U. S. Gov’t.) 
Synthetic manufacture of thymol. 6-Isopropyl 3-cresol. 

Pure 4-CYMENE is slowly added to equal weight H,SO, (1.84) below 0°, then mixed acid 7 
(HNO, (1.42): H,SO, (1.84) —1: 2) containing 5-10 per cent more HNO, than is required for 
one NO, group, keeping temp. below 0°. The purified nitro CYMENE is reduced to amino cymene ~~ 
or cymidin by Fe and HCl, converted to sulfate by mixing with 0.69 parts H,SO, (1.84) and 
“baked”? to convert sulfate into ortho or para sulfo acid, diazotized, gently reduced with alk. 
SnCl,, etc., to form 6-isopropyl 3-crEso. and Na salt of this is fused in NaOH to produce 
thymol, which is steam distilled from acidified soln. ; 


1,8334,641—Mar. 23, 1921. Jean ALTWEcG and Joanny LaAnprivon, France. (Soc. Chim.) 
Beta-halogen-ethylaminobenzoie esters and their derivatives. i 


b-Oxy ethyl 4-amino BENzoIc acid, ethyl ester, in 0.75 parts dry benzene is poured into equal 
parts PCI, also in dry benzene soln. (1.25 parts) and mixture heated at 100°. Benzene and 
POCI, are evapd. off and residue distilled under reduced pressure. Analogous esters and other 
chlorinating agents such as sulfur or thionyl halides, etc., are claimed. 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 463 


1,334,642—Mar. 23, 1920. Jean ALtwecc and Joanny Lanprivon, France. (Soc. Chim.) 
B-Alkylamino-ethylaminobenzoic alkyl esters and their derivatives. 
b-Chlor ethyl. 4-amino BENzoIc acid ethyl ester, or analog, and 2 mols. diethyl amin, or 


other alkyl amin, are heated at 100° in closed vessel for several hours, cooled, filt., and crysts. 
washed to remove diethylamin HCl. 


1,336,952—Apr. 13, 1920. Alphons Games, Switzerland. (Basle.) 
Allylester of the 2-phenylquinolin-4-carboxylie acid. A tasteless solvent for 
uric acid. 


‘2-Phenyl QUINOLIN 4-carbo, Na salt, is refluxed at 100° in 0.5 parts acetone and o.5 parts 
ALLYL bromide added. After about 6 hours the acetone and excess allyl bromide are distilled 
off, residue extracted with ether, and HCl salt pptd. from dry ether soln. by HCl. Using the 
allyl halide as solvent and passing dry HCl or adding a little conc. H,SO, and other methods 
of esterification may be used. 


1,338,297—Apr. 27, 1920. Wilhelm Grurrerign, Germany. (U. S. Gov’t.) 
Trimethyl-acetyl-salicylic-acid compounds. 


Equimols trimethyl acrtyt chloride and saticytic acid are mixed in dry ether containing 
pyridin in sufficient amount to absorb HCl that is produced, shaken, cooled, let stand 2 days, 
ether removed and crysts. filt. off and dried. Trimethyl acetyl 3-crEsorinic acid analogs can be 
made in similar way, and strontium salt prepared. 


1,347,083—July 20, 1920. Aron ECKMANN, Switzerland. (Schweiz Serum.) 


Process of producing mercuro-amino combinations. Stable mercuro amino comps. 
with pyrazolone (40 per cent Hg.) 


Phenyl 2.3-dimethyl 4-sulfamino PYRAZOLONE in aq. soln. is mixed with 0.5 to 1.0 mol. freshly 
prepared moistened Hg,SO,. The gray white cryst. substance that forms is filt. by suction, 
washed and dried at low temp. The sulfuric acid previously combined with Hg is found in 
soln. The mercuro amino salt may be converted in aq. suspension to the soluble mercuric salt 
by NaOH, Hg being deposited. 


1,350,408—Aug. 4, 1920. Max Hartman and Ernst Wysert, Switzerland. (Basle.) 
Thienylquinolin carboxylic acids. 


ACETOTHIENONE, derived from THIOPHENE and acetyL chloride, is condensed with equimol. 
ISATIN or derivs. by heating at 100° in 28 per cent KOH containing some alcohol, cooled and 
2-thienyl quinolin 4-carbo acid is pptd. by acetic acid. Or sodium salts of halogen isatin are 
refluxed in NaOH-alc. or other alk. soln. with aceto thienone. 


1,3852,082—Sept. 7, 1920. Emil MU.uer, Switzerland. (Hoffmann.) 


Homologue of tropin and the process of producing same. 

Anhydro EcGONIN is treated with sodium and amyzt alc. or is catalytically or electrolytically 
reduced in dil. acid soln. to dihydro anhydro EcGONIN, dissolved in 8 parts abs. alc., dry HCl 
added at boil and alc. evapd. off. Ag. soln. of sediment is pptd. by K,CO, resulting dihydro an- 
hydro EcGoniIN, ethyl ester, in 15 parts abs. alc. at boiling temp. is reduced by 2.4 parts Na, 
soln. made acid with HCl, alc. evapd. and homotropin extracted from alk. soln. by ether. 


1,356,877—Oct. 26, 1920. Wilhelm N. Nacar, Japan. (Bunnell.) 
Mydriatic and process of making same. A synthetic product resembling the alkaloid 
ephedrin. 


BENZALDEHYDE and nitro ETHANE are shaken several hours at usual temp. with weak alk. 
such as carbonate, bicarb., phosphates, or pyridin, etc., resulting phenyl nitro propanol sep- 
arated from excess reagents, reduced in dil. alc. acetic soln. containing formaldehyde by adding 
Zn at low temp., solvents and Zn removed and methyl amino PHENYL propanol HCl extracted by 
ether from HCl soln. It is in racemic form. 


1,358,750—Nov. 16, 1920. 
Oliver Kamm, Roger ApAMs and Ernest H. Vouwiter, Illinois. (Abbott.) 
Anesthetic compound. Dibutyl amino alcohol ester of benzoic acid or derivs. 

BeEnzoyyz chloride, homolog or deriv., in benzene soln. is refluxed with 1 mol. DIBUTYL amino 
ethyl alcohol for 1 hour, basic comps. removed by dil. acids and di-butyl amino alcohol ester of 
BENZOIC acid converted to HCl salt. Dibutyl amino ethyl alcohol is readily formed from 
ETHYLENE chlorhydrin and piIBUTYL amin. 


464 DIGEST OF PATENTS 


1,358,751—Nov. 16, 1920. 
Oliver Kamm, Roger ApAms and Ernest H. VouwieEr, Illinois. (Abbott.) 
Anesthetic compound. 


Process is similar to 1,358,750 except that the amino propyl alcohol, or homolog, is sub- 
stituted by two alkyl radicals that may be different but one of which is larger than ethyl. 


1,360,994—Dec. 7, 1920. Roger ApaAms and Ernest H. Voniwi er, Illinois. (Abbott.) 
Allyl esters of p-amino benzoic acid. Substitute for phenyl cinchonic acid. 

4-Nitro BENZOYL chloride and equimol. aLuyt alc. are refluxed 1-2 hours then vacuum distilled 
to yield the ester, which with 4 parts: Fe powd. and 30 per cent HCl is reduced at 50° and 
product extracted by ether from alk. soln. Other allyl esters of benzoic acid derivs. are de- 
rived by similar methods. 


1,861,128—Dec. 7, 1920. Mari E. Wotvexamp, Illinois. (Abbott.) 
Phenyleinchonic-acid salt. 

Phenyl cincHonic acid, 1 mol., is added to aq. soln. of o.5 mol. NaOH and suspension 
stirred and rubbed vigorously until it is of buttery consistency, is filter pressed, residue washed 
and dried below 100°. 


1,375,949—Apr. 26, 1921. Jean ALtwecc, and David Epin, France. (Soc. Chim.) 
Process for the preparation of twice-substituted 2-4-diketo-tetrahydro- 
oxazols. (Product also claimed.) 

To PHENYL ethyl oxy ACETAMID in 7 parts toluene containing about 1.5 parts anhyd. K,CO, 
is slowly added (for 2-3 hours) 0.67 parts chlor FoRMIc acid, ethyl ester, while temp. is such 
that toluene distils continuously, refluxed for 1 hour longer, aq. added, the 5-phenyl 5-ethyl 
2.4-diketo tetra hydro oxazole separated by acid and distilled under reduced pressure. Other 
materials and solvents are claimed. 


1,378,343 
Aralkyl ester of 2-phenylquinolin-4-carboxylic acid. 


May 17, 1921. Alfons Gams and Otto KaisEr, Switzerland. (Basle.) 


2-Phenyl QuINOLIN 4-carbo acid, Na salt, suspended in 4 parts acetone is refluxed on water 
bath and o.5 parts BENzyL chloride added drop by drop. After 20-24 hours acetone is distilled 
off, residue in benzene soln. is washed with carbonate till neutral, dried over CaCl,, dry HCl 
passed in and resulting HCl salt converted to free ester by alk. carb. in alc. soln. A halogen 
deriv. of the quinolin comp. and an aralky] alcohol may be used. 


1,384,637—July 12, 1921. Josef ScuHu Ler, Switzerland. (Basle.) 
Unsaturated ether of ethenylparadioxydiphenylamidin. 

4-Amino PHENOL, allyl ester, and equimol. of acetyl deriv. in benzene soln. containing 1.25 
parts PCl, are refluxed 4 hours at 100°, solvents, etc., removed, residue dissolved in hot aq., filt. 
and pptd. by NH, as ethenyl 4-dialloxy DIPHENYL amidin. Reaction takes place without solvent 
or diluent, and with POCI,, P,O,, or other phosphorus haloids. 


1,388,573—Aug. 23, 1921. Oliver Kamm and Ernest Votwi er, Illinois 


Anesthetic compound.  y-Diallyl amino propyl alcohol ester of 4-amino benzoic acid with 
properties like cocain. 
BENzoy. chloride or deriv. in benzene soln. is refluxed with diallyl amino PproryL alcohol for 
1 hour, basic comps. removed with dil. acid, the diallyl amino propyl alcohol ester of benzoic 
acid pptd. from aq. soln. with NaOH and HCI salt formed. Nitro derivs. are reduced with Sn 
and HCl at 50°. 


1,390,972—Sept. 13, 1921. 
Jay F. Scuamperc, George W. Raiziss and John A. KoimeEr, Pennsylvania. (Dermatol.) 
Oxymercury nitrophenolate. (Process also claimed.) ; 
Purified 2-nitro PHENOL is dissolved at 100° in 15 parts distilled aq. containing equal parts 
40 per cent NaOH, and 2.23 parts mercuric acetate c.p. in same vol. aq. containing a little glac. 


acetic acid are added in three portions drop by drop. First one fourth is added at 50° then 
ro cc. of 40 per cent NaOH, a second fourth added at 65°, again 10 cc. of 40 per cent NaOH 


and finally the remaining half added, temp. raised to 80° until no free HgO remains, and 


cooled to ppt. product, filt., washed, etc. 


. 
; 
. 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 465 


1,391,705—Sept. 27, 1921. Rudolf Tampacu, Germany. (Chem. Found.) 
Process for producing tannic-acid compound of the digitalisglycosids. 
An alk. soln. of digito tannates from PURPUREA is extracted with CHCl, containing some 


alc., solvent is removed, and glucoside mixture in 5 parts alc. is mixed with alc. soln. of 3 
parts tannate comps. isolated from digitalis purpurea. 


1,399,144—Dec. 6, 1921. Wilhelm N. Nacar, Japan. (Bunnell.) 
Synthetically-compounded drug product and method of producing the same. 

Methyl amino dioxy phenyl ethanol, HCl salt. 

Diacetyl PROTOCATECHUIC aldehyde, derived from ackTyt chloride and protocaTscHUIC 
aldehyde in presence of sod. acetate, is condensed with nitro METHANE in aq. alk. carb., bicarb. 
or phosphate, pyridin, etc., separated and reduced with Zn and dil. acetic in presence of for- 
maldehyde, Zn removed by H,S, and volatile comps. distilled off from HCl soln. 


1,899,312—Dec. 26, 1921. Nagayoshi Nacar, Japan. (Bunnell.) 
Synthetic anesthetic and process of making same. (Process not claimed.) 

Allocain A and §., two new alkaloids. 

MypriaTINn set free from salt by alk. carbonate, is refluxed in aq. soln. at 30-40° with 
ETHYL bromide in presence of alk. carb. The mono and diethyl derivs. result, and these in 
ether soln. are condensed with BENZoyL chloride at usual temps. Mixed benzoyl mono and 
diethyl mydriatin may be used as such or separated by shaking ether soln. with dil. HCl which 


takes up the diethyl comp. ‘“‘Allocain S” and ‘“‘Allocain A,’”? the mono ethyl comp. is recovered 
from the ether as HCl salt. 


1,403,117—Jan. 10, 1922. Max HartMann and Max SEIBERTH, Switzerland. (Basle.) 
Dialkylamides of nicotinic acid and process of making same. 

Nicotinic acid chloride is heated at 160° for 2 hours with equivalent quantity of DIETHYL 
amin HCl., aq. soln. of mass mixed with KOH (1:1) and shaken with ether which is removed 
and residue redistilled in vacuum. DIPropyz amin, piperidin or other secondary amins are 
claimed. Acid chloride of nicotinic acid is made by means of thionyl chloride. 


1,405,228—Jan. 31, 1922. Philip A. Koper, New York. (Squibb.) 
Process of making primary arsanilic acid. Primary arsanilic acid (Na salt is 
“atoxyl’’) with but small amounts secondary deriv. 


Arsenic acid, 76 per cent, is heated at 120-140° to produce 100 per cent acid, cooled to 0°, 
added to 1.5-2 mols. ANILIN at 0° or lower, ground product melted at 160°, refluxed at 160-185°, 
excess NaOH(6N) added, aq. layer separated and shaken with kaolin, filt., neut. carefully with 
HCI(6N) and crysts. filt. out. Yield is 20-30 per cent. Limiting temp. and amount of anilin 
are controlling factors in process. 


1,408,462—Mar. 7, 1922. ; Robert Marcuanp, Netherlands. 
Process for the preparation of terpineol. Terpineol from terpin hydrate by continous 
process with nearly theoretical yield. 
Terpin hydrate is heated with guINoLIN sulfo acid, or other organic sulfonic acid. 


1,408,974—Mar. 7, 1922. Louis Benpa, Germany. (Cassella.) 
Arsenical compound of the acridine series and process of making the same. 
Arsenical compound with small poisonous properties. 


3.6-Diamino 1o-methyl ACRIDIN HCl is diazotized, sod. arsenite added then excess Na,CO, 
(oN), soln. boiled, filt. and made slightly acid with HCl to ppt. crude arsinic deriv. Product 
will diazotize and couple with R-salt (R) or resorcinol (OR), etc. 


1,411,859—Apr. 4, 1922. Robert Marcuanp, Netherlands. 


Process for preparing hydrate of terpin. 

Oil of turpentine or PINENE, is mechanically mixed with H,SO, or other acid in an inert 
atmosphere such as CO, or N, agitating vigorously for 6-8 days. Oxidation is wholly prevented 
and nearly theoretical yield obtained. 


1,412,440—Apr. 11, 1922. Mari E. WotvexKamp, California. 
Chemical compound. Mono, di or tri mercuric aurin tricarboxylate, with or without NaCl 


present. 


466 DIGEST OF PATENTS 


Mixtures of AuRIN tricarbo acid, HgCl, and NaHCO, are boiled in aq. in proportions of 
1:1: 2 mols., (mono deriv.), 1: 2:4 (di) or 1:3:6 (tri). Products contain 30.7 per cent, 47.6 
per cent, or 59.3 per cent Hg respectively. For comps. free of salt, HgO is used and propor- 
tions are 1:1:2 (mono), 1: 3:2 (di) and 1:4: 3 (tri). After boiling, the soln. is made acid 
with H,SO, when HgO is used. 


1,412,937—Apr. 18, 1922. Fritz GuntHer, Germany. (Badische.) 
Manufacture of thymol. 


3-CrESoL is added to 1.6 parts H,SO, monohyd., keeping temp. below 100° for 2 hours, 
cooled to 85°, and a little more than equimol 1sopropyL alc. also in 1.6 parts H,SO, added drop 
by drop at low temp. during 40 mins. fter 3-4 hours at same temp. mass is cooled, diluted and 
distilled with steam at 120-130° whereby sulfo group is split off and thymol distils. 


1,414,383— May 2, 1922. Jean ALtwecc, France. (Soc. Chim.) 
Process for the preparation of the di-alkyl-amino-ethyl derivatives of 
theobromine. (Product, not process, claimed.) 
Chlor ethyl DIETHYL amin in benzene, or other neut. organic solvent, is boiled several hours 
with 1.34 parts THEOBROMIN sodium, cooled, filt. from NaCl and evapd. The HCl salt is formed 
by evapg. aq. soln. to dryness with equimol. HCl. 


1,415,700—May 9, 1922. Ernst PREISWERK, Switzerland. (Hoffmann.) 
Process for the manufacture of 1l-allyl-3.7-dimethylxanthine.  1-Allyl 3.7-di- 
methyl xanthine produced at atmospheric pressure. 
3.7-Dimethyl XANTHINE in 8 parts abs. alc. are stirred while 0.72 parts of 48 per cent KOH 
are added, then refluxed while adding 0.74, parts ALLyL bromide drop by drop for 2-3 hours, 
further boiled 5-6 hours, separated from alc. and t1-allyl 3.7-dimethyl xanthine recovered as 
crysts. and by extracting filtrate with CHCl,. Modifications of process are given. 


1,417,167—May 23, 1922. Markus GUGGENHEIM, Switzerland. (Hoffmann.) 
Complex silver salts of a-amino acids. (Process also claimed.) 
GLycocoL, or other alfa amino acid, in aq. soln. is mixed with freshly pptd. Ag,O, or other 


silver salt, heated, filt., cooled below 0° and coagulated by stirring. The weight of amino acid 
must be at least 5 times that of the Ag,O actually present in the silver comp. 


1,418,900—June 6, 1922. Jean ALTwWeEGG and Joanny Lanprivon, France. (Soc. Chim.) 
Process for the manufacture of new mono- and di-b-oxyethyl-amino-benzoic 
esters. (Product, not process, claimed.) 
One mol. 4-amino BENzoIc acid, ethyl ester, and 1 or 2 mols. of ETHYLENE oxide are heated 
at 50° for several hours in closed vessel and product distilled under reduced pressure. Small 
quantities of aq. or alc. accelerate the reaction. 


1,419,092—June 6, 1922. Otto Wo.Fes and Horst Marner, Germany. 


Preparation of tropinone monocarboxylic-acid esters. (Product also claimed.) 

Succinic dialdehyde, 17 parts, dissolved in 170 parts aq., is stirred with mixture of 40 
parts aceto ACETIC ester with 24 parts alkali and 12 parts METHYL amin in 200 parts aq., cooled, 
after 5 hours K,CO, added and shaken with CHCl,, from which basic products are recovered 
by shaking with acid and pptg. acid soln. by Na,CO,. Yield is about 20 per cent. 


1,422,294—July 11, 1922. Chester N. Myers, New York. (Metz.) 


Complex arseno-stibino compounds and process of making the same. 4.4’- 

Dioxy 3.3’-diamino arseno stibino comps. or N-derivs. thereof. 

3-Nitro 4-oxy PHENYL arsinic acid and corresponding stibinic acid are converted to Na salts 
by mixing at 45° in aq. soln. with NaOH then in equimols are reduced with sod. hydrosulfite, or 
other reducing agent at 3°, preferably in presence of MgCl,. Product may be converted to di- 
hydro-chloride by HCl in methyl alc. soln. and this salt further treated in alc. soln. with sod. 
sulfoxylate, which substitutes in one or the other amino groups, or the hydrogen of the amino 
groups may be replaced by other radicals. 


1,422,869—July 18, 1922. George KRANZLEIN and Martin Corgeti, Germany. (Hochst.) 


Esters of dioxy diethyl sulphide and process of making same. 
Acids are caused to react upon dioxy pIETHYL sulfid, using acids of weak or amphoteric 
character to avoid formation of diethylene oxide sulfid by closing the ring. Refluxing at 120° 


ee a eH ee re Se ee 


iy 


| 
‘ 


_s 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 467 


in acetic anhyd. soln. or in 90 per cent formic acid or in case of dithio cLycoL, heating in 
vacuum with 2N H,SQ, or 5 per cent Al(OH),, are examples given in patent. 


1,423,101—July 18, 1922. Alfons Gams and Ernest Wysert, Switzerland. (Basle.) 


Process of preparing optically-active aromatic aminoalcohols. Dextro and 
laevo 2.6-dioxy phenyl methyl amino ethanol, etc. 


Methyl amino aceto PYROCATECHOL or ethyl deriv. and equimol d-TarTaRiIc acid are dissolved | 
in large volume aq., colloidal platinum added and shaken with H until sufficient has been ab- 
sorbed, Pt removed, soln. evapd. partly, filt., evap. dry and methyl alc. soln. of residue in- 
oculated with a crystal of /-salt which latter separates and the d-salt remains in soln. Ag. soln. 
of /-salt deposits free base by addition of NH, which base corresponds to “adrenaline.” The d- 
base is separated in similar way. 


1,424,236—Aug. 1, 1922. Jurgen Catutsen, Germany. (Bayer.) 

Manufacture and production of bromodiethylacetylearboxalkyl-urea com- 
pounds. (Product, not process, claimed.) Brom diethyl acetyl urea carbo acid, ethyl 
ester. 


Bromo diethyl acEtyL isocyanate is heated at 100° with equimol. ethyl URETHANE and re- 
sulting oil cryst. from pet. ether. 


1,425,929—Aug. 15, 1922. August ALBert. Germany. 
Derivatives of organic arsenic compounds. Arseno hydrazone. 


ACETOPHENONE arsonic acid, propionphenone arsonic acid or analog is treated in acid, alk. 
or neut. soln. with HYDRAZIN or its alphyl or as-dialphyl deriv. 


1,425,930—Aug. 15, 1922. August ArsEert. Germany. 
Process of manufacturing new arsenic oxides or arsenobenzols. (Product 


also claimed.) 


Arsonic acid derivs. claimed in 1,425,929 are reduced in alk. soln. with hydrosulfite, PCl,, 
etc., to the oxide form of trivalent arsenic or still further reduced to the bis arseno deriv. 


1,425,931—Aug. 15, 1922. August ALBERT, Germany. 
Method of producing new aromatic compounds eontaining carbonylgroups 
with trivalent arsenic. (Product also claimed.) 


Arsonic acid comps. of aromatic series, such as BENZALDEHYDE arsonic acid, containing one 
or more carbonyl groups in noncyclic linkage, may be reduced by hydrosulfite, etc., in the arsenic 
group only as in 1,425,929-30, to the trivalent bis=arseno comp. 


1,426,348—Aug. 22, 1922. Max Bocxmiiut and Kurt Winpiscu, Germany. (Hochst.) 
Methyl sulphites of secondary aromatic aliphatic amines and process of 
making same. N-Methyl 4-phenetidin methyl sulfite, homologs and analogs. 
Three parts FORMALDEHYDE, 10.4 parts NaHSOQ, and 15 parts N-methyl 4-PHENETIDIN in 25 
parts alc. are boiled till soln. is homogeneous. Reaction product separates on cooling. Other 
secondary aromatic aliphatic amins are claimed. 


1,427,506—Aug. 29, 1922. Richard WiiistArter and Walter DuIsBERG, Germany. (Bayer.) 
Urethane of the trichloroethylic aleohol. 
Trichlor ETHYL alcohol and carBaMic chloride in equimols. are mixed in ether soln. 


1,429,922—Sept. 26, 1922. Max Bocxmtuy and Adolf Scuwarz, Germany. (Hochst.) 
Aliphatic dialkylamino alkyl compounds and process of making same. 
a-Diethyl amino ethyl aceto acetic, ethyl ester. 
Equimols. of chlor ethyl DIETHYL amin and aceto ACETIC, ethyl ester, are stirred while 
caustic alk. is added, product dissolved in benzine, shaken with NH,, dried and fractionally 
distilled under reduced pressure (10 mm.). Other related comps. are claimed. 


468 DIGEST OF PATENTS 


1,431,863—Oct. 10, 1922. Jean ALTweEcc, France. (Soc. Chim.) 
Process for obtaining calcium salt of acetyl salicylic acid. 


Acetyl SALICYLIC acid soln. is neut. with calc. amount Ca(OH), in presence of common 
salt, which prevents saponification. 


1,432,291—Oct. 17, 1922. Oscar Hinsperc, Germany. 
a-Oxyaryl-substituted b-aminoethanes and process of making same. 

Amino ACETAL and 2 parts PHENOL in glac. acetic soln. are gradually mixed, while cooling, 
with 4.5-7 parts conc. H,SO,, let stand several hours, diluted and neut. with NH, or Na,CO,. 
Other phenols, such as thymol, 3-amino phenol, pyrocatechol or pyrogallol, etc., may be used, 
also conc. HCI instead of H,SO, and methyl amino acetal or derivs. 


1,432,298—Oct. 17, 1922. Max Puriiyips, Wisconsin. (U. S. Gov’t.) 
Manufacture of synthetic thymol. 

Cymipin sulfo acid, which in 1,332,680 is diazotized and reduced with SnCl, or CH,O, and 
Cu, then fused in NaOH, in current patent is reduced by conc. NaHSO,, made acid with HCl to 
produce cyMyL hydrazin 3- or s-sulfo acid, the hydrazin group removed with CuSO, or FeCl,, 
and residual cyMENE 3-sulfo acid fused in caustic alk. to convert into thymol. 


1,434,306—Oct. 31, 1922. Karl Mirscuer, Switzerland. (Basle.) 
Amincalcohol of the quinoline series and process of making same. (Process 

not claimed.) Dimethyl amino 2-phenyl 4-quinolyl ethanol, and analogs. 

2-Phenyl QUINOLIN 4-carbo acid, or deriv., is changed to the 4-alkyl ketone by condensing 
its esters with esters of fatty acids in presence of sod. ethylate and splitting off the ketone by 
acids. Or the 4-nitrile can be decomp. by Grignard reaction. Ketone is then halogenated, com- 
bined with an amin to an amino ketone and reduced to an ethanol deriv., or the iso nitroso comp. 
is formed and reduced. 


1,436,304—Nov. 21, 1922. Alfred S. Burpicx and Elmer B. VureEr, Illinois. (Abbott.) 
Benzyl ester of acetyl salicylic acid. 


BENZYL salicylate, 1 mol., is heated in oil bath at 140° with 1.3 mol. acetic anhyd. and 
1.5 mol. anhyd. sod. acetate, cooled product triturated with benzene and aq. and benzene soln. 
dried, fractionated under reduced pressure, collecting fraction at 170-200° and 5 mm. press. 
Benzyl acetyl salicylate crysts. on cooling. 


1,437,802—Dec. 5, 1922. Max HarrMann and Hans Kaci, Switzerland. (Basle.) 
Derivatives of dihydroisoquinolin. 


a-Acidyl amino CINNAMIC ester, or deriv. substituted in the nucleus, is hydrogenated, using 
Ni or Pt catalyst and dihydro product condensed with or without solvent to a quaternary am- 
monium salt such as 1-phenyl 6.7-methylene dioxy 3.4-dihydro iso quinolin 3-carbo, methyl 
ester. 


1,439,605—Dec. 10, 1922. Mortimer Byr and Lewis H. Caritson, Michigan. (Stearns.) 
Medicinal preparation. Succinic acid, dibenzyl ester. 


Succinic acid and BENZyL alcohol are refluxed. at 185-195°, cooled, residual succinic acid 
filt. off and filtrate vacuum distilled above 200° at 15 mm. Residue, containing unchanged ma- 
terials, is treated with 5 per cent alc. or other solvent, frozen in ice bath to cryst. benzyl suc- 
cinate, filt., etc. 


1,440,652—Jan. 2, 1923. Roger Apams and Ernest H. Votwiuer, [llinois. (Abbott.) 
N-Butyl esters of para amino benzoie acid. 


4-Nitro BENzoIc acid and 2.5 parts BUTYL alcohol are refluxed with 0.16 parts conc. H,SO,, 
vacuum distilled to recover excess alc., residue in dil. Na,CO, soln. extracted with ether, etc., 
and purified nitro ester is reduced in 20 per cent HCl with 4 parts powd. Fe at temp. of 50°. 
Diamino derivs. and other n-butyl esters are claimed. 


1,459,900—June 26, 1923. Mark E. Putnam and John MccreapiE, Michigan. (Dow.) 
Methed of making salicylates. Removing color from crude salicylates with consequent 
increased yields. 


SauicyLic acid is neut. with sod. carb. or bicarb. by usual process and before concentrating 
a small quantity (0.5 per cent of salicylate present) of tin salicylate, preferably the stannous 


5 
q 
it 
) 


a? feel 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 469 


salt, or SnCl, or PbCl,, is added, soln. heated, and H,S passed through. Organic colored im- 
purities are carried down with the pptd. sulfide leaving a clear soln. of sod. salicylate, which 
must be slightly acid, and after filtg. and evapg. all of the salt is recovered as a flaky white ppt. 


1,472,298—Oct. 30, 1923. Casimir Funx and Louis FreEpMAN, New York. (Metz.) 
Derivatives of suprarenin and process of preparing the same. 

One part of racemic SUPRARENIN HCl or base is refluxed 2-5 hours with 10 parts absolute 
ethyl alc. containing 1-4 mols. dry HCl. Two products, resulting from the action of alcohol on 
suprarenin and about 10 per cent of a comp. of higher molecular weight (probably 2 mols. 
suprarenin combined as a lactone) are separated by frac. crystn. from abs. alec. 


1,474,567—Nov. 20, 1924. 
Werner ScHULEMANN, Ludwig Scuttz and Kurt MeEIsENBuRG, Germany. (Bayer.) 

Ester of substituted amino propyl aleohol. y-Dialphyl a.b-dialkyl propyl] alcohol. 

One mol. a-methyl b-methyl y-dimethyl amino Propyy, alc. mixed in 4 parts benzene with 1 
mol. 4-nitro BENzoyL chloride is heated at 100°, water added and benzene separated. Addition 
of Na,CO, soln. ppts. 4-nitro benzoic acid ester of the alcohol. One part of this in 3 parts conc. 
HCl is reduced by 1 part Sn at 60°, metal separated by H,S and organic base pptd. by carbonate. 
Other esters are claimed. 


1,476,934—Dec. 11, 1923. Ernest H. VotwiLeR and Roger Apams, Illinois. (Abbott.) 


Anaesthetic compound. y-N-Butyl amino propyl alcohol ester of 4-amino benzoic acid. 

One mol. y-brom propyl 4-nitro BENzoIc acid ester mixed with 2 mols. N-BuTy. allyl amin 
is heated to 60° for 3 hours. Water and benzene are added to mixture and layers separated. 
Benzene layer is extracted with HCl, solution treated with Sn at 50°, tin removed and base re. 
covered from soln. by addition of alkali. Other compounds claimed. 


SUBGROUP (p).—PHOTO CHEMICALS. 


604,049—May 17, 1808. Paul JAcoBson and Herman Ticcrs, Germany. (Cassella.) 


Oxydiamidodiphenyl and process of making same. 4.2’-Diamino 5-oxy dipheny]. 

Acetyl oxy azo BENZENE, finely ground, is added to 6 parts 38 per cent HCl—4o per cent 
SnCl, soln. keeping temp. below 40°. The SnCl, double salt of oxydiamino diphenyl is pressed 
free of HCl, the Sn pptd. by H,S in aq. soln., evap. in atmosphere of CO,, benzidin pptd. by dil. 
H,SO,, filt. and oxydiamino diphenyl pptd. by Na,CO,. Product is useful as intermediate or 
photo developer. 


729,054—May 26, 1903. Friedrich FiscHer and Hugo Guntrum, Germany. (Elberfeld.) 
Amido-oxybenzyl sulfonie acid. 3-Amino 6-oxy benzyl w-sulfo acid. 

3-Nitro 6-oxy BENZyL chloride, produced as shown in 696,020, is mixed at usual temp. with 
1.34 parts NaHSO, in 1o parts aq., filt., pptd. by acid and salt, reduced by boiling in 2 parts aq. 
with Zn dust or equivalent, filt., and pptd. by HCl. Product is stable in air and is of especial 
value as photo developer. 


767,815—Aug. 16, 1904. Benno Homoixa and Nicholaus Schwan, Germany. (Hoéchst.) 
Photographie developer. Alkali salt of glycocoll as harmless alkaline agent in developing 
bath. 


Aq. soln. containing 8 per cent cryst. NaHSO,, 1.2 per cent PYROGALLOL, or 1.1 per cent 
hydroquinone, etc., mixed with 2.4 per cent glycocol and 1.2 per cent NaOH may be used directly 
as developer of dry plates of brom-silver gelatin or diluted for chlorbrom-silver plates or paper. 
Alk. bromide will help to clarify. Images form rapidly, are clear and gelatin does not curl or 


float. 
922,040—May 18, 1909. Paul REHLANDER, Germany. (Chem. Fab.) 
Aralkyl-para-aminophenol. (Process also claimed.) Benzyl 4-aminophenol and related 


comps. 
Benzylidene 4-amino PHENOL, or the anisylidene or salicylidene deriv., is hydrogenated in 


alk. soln. with Zn dust, neut., decanted and solid pptd. extracted with ether. 


1,297,685—Mar. 18, 1919. Rolla N. Harcer, District Columbia. (U. S. Gov’t.) 
Process of manufacturing n-methyl p-amino phenol. Improved process for “metol. ’ 


METHYLAMIN, prepared by methylating NH,Cl with 40 per cent FORMALDEHYDE and setting the 


base free with NaOH or Ca(OH),, in 10 N soln. is mixed with equal parts HYDROQUINONE and 


470 DIGEST OF PATENTS 


* 


heated in autoclave at 150-200° for 2-5 hours. Patent gives results of many experiments in 
varying temps., pressures, ratio of ingredients and time of heating. 


1,316,804—Sept. 23, 1919. Emil Reser and Josef Srecwart, Switzerland. (Basle.) 
N-monoarylsulfo-monoalkylamino-oxyaryl compounds able to be trans- 


formed into monoalkylamino-oxyaryl compounds and process of making 
same. 


4-Amino PHENOL, ditoluene disulfo ester, is dissolved at 60° in 3.26 parts 3.5 per cent NaOH 
to form cryst. Na salt which is heated at 1o0-120° for several hours in autoclave with 2.3 parts 
METHYL alc. and a little CH,Cl or (CH,), SO,. Corresponding esters of other alkylated amino 
phenols or naphthols are claimed. 


1,326,973—Jan. 6, 1920. Ludwig Scumipt, Germany. 
Process for the preparation of pyrocatechin aldehyde. 


PIPERONAL and thionyl chloride, 1 mol. each, are heated at 100° to form piperonal dichloride 
and SO, and 1 mol. Cl from steel cylinder of compressed gas is passed into the soln. to form 
dichlor piperonyl dichloride which, when decomp. by aq., gives pyrocatechin aldehyde that may 
be extracted with ether or soln. boiled down. SO, does not interfere with action of Cl, thionyl 
chloride and Cl can be added simultaneously and solvent such as CHCl, may or may not be used. 


1,421,869—July 4, 1922. Harold von Bramer, New York. (Eastman.) 
Process of making hydrochinon. 


Dichlor BENZENE is heated at 130-140° in 2 parts com’l. oleum to form sulfo deriv., poured 
into 3 parts ice water, steam distilled to remove unchanged dichlor benzene, NaCl added to form 
Na salt which is filt. out and heated at 175-200° under pressure in an autoclave with 3.75 parts 
of 40 per cent NaOH for 24 hours. After making acid, hydrochinon is extracted from the melt 
with ether. About a 50 per cent yield is obtained. 


1,434,429—Nov. 7, 1922. Hans T. Ciarke, New York. (Eastman.) 
Process of manufacturing certain acetyl methyl amines. Methyl 4-amino phenol 
sulfate. 


Dimethyl 4-amino PHENOL, which is a by-product in the mfr. of mono methyl 4-amino phenol, 
is converted to the acetate by warming with acetic anhyd. and the acetate at 190° is treated 
with AcEetTyL chloride, keeping above 160° or the critical temp. Methyl chloride is evolved and 
acetyl methyl 4-amino phenyl acetate is distilled under reduced pressure (12 mm.) at 196°. 
Treated with dil. H,SO, cold then boiling removes the two acetyl groups and forms the sulfate 
of methyl 4-amino phenol. 


SUBGROUP (pl).—PLASTICS. 


900,744—Oct. 13, 1908, Isidor Krtses, Pennsylvania. 
Method of producing cellulose compounds. 
Improvement in CELLULOSE comp. useful for jars and electric resistance. 


1,088.677—Mar. 3, 1914. Leo H. BarKeLtanp, New York. (Bakelite.) 
Infusible condensation product of metacresol and formaldehyde. 


The essential constituents are confensation products of FORMALDEHYDE and 3-crEsoL and of 
formaldehyde and PHENOL compounded with a filling material and containing corresponding con- 
densation products of 4 and 2-crEsoL only in minor proportions. 


1,088,678—Mar. 3, 1914. Ljeo H. Barxetanp, New York. (Bakelite.) 
Infusible condensation product. 


An insoluble and infusible body containing essentially the condensation products of FORMAL- 
DEHYDE and 3-crESOL, 4-cresol, and PHENOL compounded with filling material, the condensation 
products of 3-cresol and phenol being in preponderating proportion. 

See 942,699; 942,700; 942,852; 942,808; 942,809; 939,966; 941,605; and 949,671. | 


1,236,917—Aug. 14, 1917. Marc Darrin, Pennsylvania. (Koppers.) 
Method of recovering resins from benzol plant residue. 


Benzoy plant residues are dissolved in light oils, solvent naphtha, etc., distilled to determine 


vapor temp. (150-300°) and gaseous fluid such as steam, air, or other, is blown thru soln., which — 


i 
th 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 471 


is maintained at same temp. The melting point of resin product depends on temp. of distn. 
and duration of. blowing operation. 


1,263,813—Apr. 23, 1918. Frederick W. Sperr and Marc Darrin, Pennsylvania. (Koppers.) 
Manufacture of resins. 


Resins are produced from comps. of the COUMARONE or INDENE group especially crude 
solvent naphtha from gas, tar or petroleum, by heat and pressure (50-300 lbs.) in presence of 
a catalytic metal (Cu, Ag, Au, Pt), then distilling at 150-300° and blowing air thru to remove 
volatile uncondensed material. 


1,294,662—Feb. 18, 1919. Henry S. A. Hout and Gerhard Sreimmic, Germany. (Badische.) 
Producing substances resembling caoutchouce. 


Polymerization of 1.3-BUTADIENE and homologs such as ISOPRENE etc., can be accelerated 
and yield increased if about 3 per cent of an organic substance containing oxygen loosely 
combined, such as peroxides, superoxides, ozonides, ozonized caoutchouc or butadiene, terpene 
or benzoyl peroxide, etc. be present. 

Note 1,189,110. 


1,294,836—Feb. 18, 19109. Karl Scuiatrer, New Jersey. 
Oxidation product of cumarin and indene. (Process also claimed.) 


To a soln. of CUMARIN Or INDENE comp. in CCl, about 4 per cent chromyl chloride in same 
solvent is added at usual temp. Gum or turpentine, oils, etc., may be present and other 
oxidizing agents are claimed. 


—1,297,328—Mar. *8, 19109. Marc Darrin, Pennsylvania. (Koppers.) 


Resin and process for manufacturing the same from crude solvent. Prac- 
tically pure light colored resin of para coumarone, homologs and para indene. 


Crude solvent NAPHTHA is treated with H,SO, of sufficient strength, 4 per cent of 50° acid, 
to polymerize the dark resin forming bodies without attacking cumarones or indenes, the 
latter are distilled over with other volatile oils, distillate polymerized with conc. H,SO, (0.4 per 
cent of 65° acid), neut. with NaOH or other, aq. layer separated and volatile oils distilled 
from resin or evapd. by blowing process of 1,236,917. 

Note 1,263,813. 


1,306,681—June 17, 1919. Leo H. BaEKELAND, New York. (Bakelite.) 
Phenolic condensation product and process of making same. 


A fusible body or molding mixture consists of 2- or 4- CRESOL or of several phenolic bodies 
containing excess para cresol and a substance containing a mobile methylene group such as 
HEXAMETHYLENE: tetramin, FORMALDEHYDE, etc. ‘The property of 2- and 4- cresol to react 
more slowly in the formation of an infusible condensation product is employed by having 
an excess of these present and so modifying temp. and duration of reaction as to produce 
a plastic material. 

Note 1,088,677-8. 


1,810,087—July 15, 1910. 
Lawrence VY. Repman, Archie J. Weitu, and Frank P. Brock, Illinois. (Redmanol.) 
Process of producing phenolic condensation Prndactss 


Three parts 40 per cent FORMALDEHYDE and 5 parts PHENOL are mixed and boiled at atmos. 
press. from 60-120 hours according to product desired. ‘The two layer mixture of a viscous 
creamy mass under water containing excess formaldehyde is boiled until the latter disappears, 
water is removed, gummy mass again heated above 100° with more 40 per cent formaldehyde, 
poured into molds and further heated below 100° until anhydrous, then above 100° for short 
period. 


1,310,088—July 15, 19109. 
Lawrence V. Repman, Archie J. Weitu, and Frank P. Brock, Illinois. (Redmanol.) 
Process of producing phenolic condensation products. Phenolic condensation 
products that can be sawed, machined, etc., and are transparent; for use in pipes, cigar 
holders, etc. 
Three parts 40 per cent FORMALDEHYDE and 5 parts PHENOL are boiled until the upper aq. 
layer is free of formaldehyde, aq. layer discarded, gummy mass mixed with 2 parts formaldehyde 
at 60-70° and heated to 115° until gelatinous, then poured in molds and heated at 125-150° 


472 DIGEST OF PATENTS 


until hard, resistant, insol, and anhyd. Less time is needed than when temp. is 100° and product 
is superior especially in color which is clear, light amber. Before pouring into molds dyes, waxes, 
mica, etc. can be added to produce desired effects. 

Note 1,188,014. 


1,323,589—Dec. 2, 19109. Louis GortscHaLK, New Jersey. 


Process of synthetically producing rubber or like substances. Rubber from 

limonene by more rapid and less expensive process. 

Apparatus is shown whereby turpentine from which resin has been removed passes from 
a container thru a vaporizing vessel at 225-240° and a tube in an oven at 250°, where PINENE 
is changed to LIMONENE which as gas, bubbles thru molten Na where it becomes rubber and 
with other vapor and gases is carried to a condenser and recovered in liquid form. About 95 
per cent limonene is converted to rubber like material. Apparently the Na does not change 
and may be used indefinitely. 


1,826,579—Dec. 30, 1919. Marc Darrin, Pennsylvania. (Koppers.) 


Resin. Pyro-para-coumarone resin, containing polymer from hydro indene. 

Patent claims products for processes given in 1,236,917 and 1,263,813. Solvent NAPHYTHA is 
polymerized by heat and the properties and merits of resulting resin are compared with resins 
produced by acid condensation. 


1,845,694—July 6, 1920. 
Lawrence V. Repman, Archie J. Weitu, and Frank P. Brock, Illinois. (Redmanol.) 
Process of producing a phenolic condensation product. 
Claims are more specific than those of 1,310,088 but cover same products. 


1,353,220—Sept. 21, 1920. 
Howard N. Copruorne, Illinois, and Arthur L. Tanneuiti, Indiana. 


Process of producing artificial resin. Resin in solution from light coal gas or coal tar 
oils. 

Solvent NAPHTHA fraction 150-200° mixed with equal amount of lighter fraction under 
130° is agitated with 1.37 per cent H,SO, (66°). The heavier oil is polymerized and remains 
in soln. in the unchanged lighter oil. Acid settles well and is drawn off, material is then neut. by 
alk. such as 1.5 per cent CaO or better by NH, gas and salt also will readily settle out. Resin 
in soln. may be used as varnish etc. or can be recovered by distillation. 


1,354,154—Sept. 28, 1920. Leo H. BAEKELAND, New York. (Bakelite.) 


Potentially-reactive composition and process of making same. 

Mixture of methylene amin PHENOL and NOVOLAK resin are heated to bring about part re- 
action, and part elimination of NH,, carefully controlling the temp. The soft, reactive pro- 
duct, called “A” has many applications. Further heating yields a hard resin of infusible type. 
Other components, diluents, solvents, etc., are claimed and detailed properties of varied pro- 
ducts are given. 

Note 1,029,737, 1,038,475, 1,187,230. 


1,355,834—Oct. 19, 1920. Hanns Joun, Czechoslovakia. 


Manufacture of aldehyde condensation product capable of technical utili- 
zation. (Product also claimed.) 

Five or 6 parts 40 per cent FORMALDEHYDE and 1 part CARBAMID or deriv. are distilled until 
sufficient liquid has been removed, then further heating at 80° converts soft preduct into resins 
of desired degrees of hardness. No condensing agent is used and temps. are higher than in 
previous patents. 


1,360,665—Nov. 30, 1920. Stuart P. Mriuer, Pennsylvania. (Barrett.) 


Process of producing resin. Coumarone resin in high yields. 

NAPHTHA containing COUMARONE, INDENE or other comps. of this series is washed with H,SO, 
of not over 77 per cent to remove color forming impurities, etc., washed oil cooled to 20° or 
preferably lower than o° and polymerized by AICI, or by H,SO, above 77 per cent, usually 
about 93 per cent. Yields are higher when temps. are kept low. 


1,865,423—Jan. 11, 1921. Stuart P. MrinxEer and Frederick H. Ruopsrs, Pennsylvania. (Barrett.) 


Production of resin. Prevention of emulsions in cleansing resins. 
After neutralizing the polymerized resin it is washed with dil. acid, preferably 3 per cent 
HCl. 


tee Bs) PAd 


£ 
a 
; 


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GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 473 


1,368,867—Feb. 15, 1921. Arthur W. WELLER and William T. Rosin-Binpiey, England. 
Phenol-formaldehyde condensation product and the production thereof. 
Condensation product is made from crkEsyLic acid or other’ phenol and FORMALDEHYDE in 


presence of CELLULOSE acetate or nitro-CELLULOSE, not over 0.7-0.8 per cent of phenol used. The 
former imparts toughness and the latter lightens the shade of the resulting resin. 


1,369,352 Feb. 22, 1921. Fritz Potnax, Austria. (Chem. Found.) 


Process for making light colored, air and light proof condensation products 
from phenol and formaldehyde. 


PHENOL cryst., homolog or deriv., is refluxed with 0.8 parts FORMALDEHYDE or polymer and 
0.002 parts sod. phenolate, resinous layer separated and repeatedly washed with 1 part aq., the 
soap like mass then washed with 10 per cent methyl alc. or 3 per cent H,O,, again with cold aq., 
distilled in vacuum to remove last traces of unchanged phenol and heated at 95-120° to convert 
into infusible, insol. product. 


1,874,526—Apr. 12, 1921. 
Lawrence V. RepMaAN, Archie J. WeITH, and Frank P. Brock. (Redmanol.) 
Process of producing a phenolic condensation product. 
Equal parts 40 per cent FORMALDEHYDE and PHENOL are boiled without condensing agent, 


upper layer containing ro per cent formaldehyde discarded, lower layer of viscous, gummy ma- 
terial heated-for a long time below 100° then for a short time above 100°. 


1,375,959—Apr. 2, 1921. Byron B. Goipsmitu, New York. 
Process of producing condensation products. (Product also claimed.) 

PHENOL and HEXAMETHYLENE tetramin are polymerized in presence of xylol or other solvent 
of suitable b.p. Temps. of 105—-165° can be applied without injury to product, and solvent can 
be readily separated from resin. Small amounts of solvent give resinous, while large excess 
give pulverulent products. Other components are claimed. 


1,389,791—Sept. 6, 1921. Arthur L. Tanneuiuy, Indiana. 
Process of producing artificial resin. 

Solvent NAPHTHA of b.p. 150—-200° is treated with small portions NaOH, shaken, allowed to 
settle, and extract drawn off. Phenols and color forming components are removed. Sulfuric 
acid is added slowly (2 per cent of 66 per cent acid), stirred 4-5 hours, let settle 3-4 days and 
separated product, which contains about 50 per cent resin, is neut. by passing NH, gas for 
several hours, heated to 60°, allowed to settle and (NH,),SO, removed. Resin is suitable for 
varnish, etc. 


1,395,968—Nov. 1, 1921. Stuart P. Minuer, Pennsylvania. (Barrett.) 
Method of preparing resin. Preventing emulsions while washing resins. 


The polymerized resin is neutralized then washed with 3 per cent by volume of 20 per cent 
NaCl. Separation of wash soln. is much more rapid than when water alone or weak salt soln. 
is applied. Later washings may be with 3 per cent NaCl or with aq. 


1,397,144—WNov. 15, 1921. Hermann Prauson, Germany. (Rotman.) 
Manufacture of artificial wood or other plastic bodies. (Product, not process, 
claimed.) ; 


Equal parts 30 per cent FORMALDEHYDE and ground wood, peat, straw, cellulose, paper or 
the like, are mixed with 0.58 parts acetone and if desired, with cement, graphite, glass powd., 
earth or metal colors, etc., and NH, gas passed in at 1-3 atms. pressure. In 10-15 min. NH, is 
removed, and aq. evapd. in vacuum. Resulting dry powd. can be pressed or stamped into forms 
at 150-500 atms. and 120-200° temp. 


1,398,146—Nov. 22, 1921. 
Emil E. Novotny, Pennsylvania, and Donald S. Kenpaut, New Jersey. (Stokes.) 
Synthetic resin composition. (Process also claimed.) 

PueENo, and FrurFURAL, furfuramid, etc. (15-40 parts) are polymerized with an acid catalyst 
such as 5-10 per cent of 39 per cent HCl, neut., washed and treated with a hardening agent 
such as hexamethylene tetramin or furfural and NH, or furfuramid, at 93-175°, with or without 
pressure. : 


474 DIGEST OF PATENTS 


1,408,826—Mar. 7, 1922. Hermann Priauson, Germany. 
Process for the manufacture of hexamethylene tetramine. 


METHANE mixed with 2 vols. oxygen, or the equiv. volume of air, and 0.67 vol. NH, is 
passed through a copper tube (Ag, Ni-steel, Fe or alloys, Sn, Zn, Al, Si, or Fe coated with one 
of these metals may replace Cu.) at 500-700°, better at low pressure or not higher than 300—500° 
at common pressure. About 8-15 cm. of the tube are constricted, say 15 mm. diameter flattened 
to 1-2 mm. Yield is 70 per cent and can be improved by previously passing gases through methyl 
or ethyl alc. at 50°. 


1,414,139 


Process of manufacture of products of condensation from phenol. Polymeriz- 
ing first with acid then with at least 10 per cent excess alkali. 


Apr. 25, 1922. Karl Kuias and Curt Pautinc, Germany. 


CrEsoL or other phenol with 0.5 parts 40 per cent FORMALDEHYDE are boiled 10-15 m. with 
0.03 parts acid (HCl 1.5), cooled, then 2.4 parts cresol, 1.2 parts 40 per cent formaldehyde, 0.2 
parts NH,, 0.05 parts each of NaOH and KOH as soln. of 1.4 sp. gr., added and mass cooled 
30 m. with reflux condenser. Resin when separated and cooled to solid is brittle mass that is 
plastic when warmed. 


1,415,468—May 9, 1922. Hermann Pravuson, Germany. 
Process for manufacture of rubber like substances 


Hydrocarbons of BUTADIENE series are polymerized at temps. not above normal by employing 
pressure of 50-600 atms. in presence of nitrogen or of a volatile liquid diluent such as NH,, 
benzene or an aq. emulsion of 1.3 per cent albumen, gelatin, etc. Higher pressures and temps. 
accelerate polymerization. 


1,416,062—May 16, 1922. Louis Rapinovitz, New York. (Ellis-Foster.) 
Coumarone resin and process of making same. 


Aromatic hydrocarbon liquids are polymerized by adding gradually H,SO, of 66° in absence 
of dil. acid and, after neutn. and washing, product is distilled under a vacuum of 29 in. to re- 
move solvent NAPHTHA while at the same time hardening the resin. 


1,418,771—June 6, 1922. Clayton W. BreprForp and Robert L. SistEy, Ohio. (Goodyear.) 
Art of vulcanizing caoutchouc. (Product also claimed.) Catalyst for vulcanizing 
caoutchouc. ; 


4-Nitroso dimethyl ANILIN is dissolved in benzol or aq. and saturated with H,S. One or 2 
mols. H,S react to form two strong basic amino comps. of different character, the former 
apparently containing sulfur as part of molecule, and it is this comp. made with less than 2 mols. 
H,S that is an active catalyst for vulcanizing processes. 


1,418,772—June 6, 1922. Clayton W. Breprorp, Ohio. (Goodyear.) 
Art of vulcanizing caoutchouec. Accelerator for vulcanizing caoutchouc. 


Methylene DIPHENYL diimin (C,H,.NH),.CH,, or other anhydro reaction products of alde- 
hydes and primary amins, is heated with 0.33 parts S at 120-150° until about 0.17 parts H,S 
are eliminated then steam distilled to remove the mol. of anilin produced. Other proportions of 
S are used and methods of applying resultant accelerators in mfg. of rubber are given. 


1,420,399—June 20, 1922. Roland IL. Anpreau, Delaware, (du Pont.) 
Process of making acetyl isoborneol. 


Glac. acetic acid (97-99 per cent) mixed with 1.5 per cent of 95 per cent H,SO, and 0.40 
parts CAMPHENE or other terpene is heated at 55-66° for 3 hours then 0.025 parts anhyd. sod. 
acetate stirred in and excess acetic acid distilled over in vacuum. Na,SO, is filt. or washed out. 
Formic, propionic or similar acid can be used instead of acetic and phosphoric or other mineral 
acid for sulfuric. 


1,422,506—July 11, 1922. Morris lL. Werss, NewYork. (Dovan.) 
Process of making diphenylguanidine. 


THIOCARBANILID, derived from 65 parts CS,, 1 part S and 120 parts ANILIN at 35-40° from 
which excess CS, is removed and residue dried, is added to 60 gals. alc. (0.85-0.90) containing 
50 lbs. NH,NO, in closed vessel, heated to 50°, z00 lbs. PbO added and temp. raised to 75°. 
The PbS is removed, alc. soln. distilled to sp. gr. of 0.95 then boiled with 125 gals. aq. Poly- 
merized diphenylguanidin remains undissolved. 


fy 
& 
rn 


i 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES 475 


1,424,137—July 25, 1922. Louis WeEIsBERG and Ralph S. Porrer, New Jersey. (Barrett.) 


Polyglycerol resin. (Process also claimed.) Reducing time and cost of resin manufacture. 

Polyglycerols, polyglycols, etc., are formed by heating the corresponding polyhydric alcohol 
GLYCEROL, etc., with a condensing agent such as 0.5 per cent of NaOH, or sod. acetate, at 280° 
or other suitable temps. Such polyglycerols when used with pHTHatic anhyd. or other di or 
polybasic aromatic or alifatic acids (diphenic, 1.8-naphthalic, benzoyl benzoic, etc., or maleic, 
succinic, tartaric, etc.) shortens the time required for all stages of condensation of resins of 
varying hardness, solubility, fusibility, etc. 


1,427,386—Aug. 29, 1022. Siegfried Hiiprert, Germany (Hilpert.) 
Process for the treatment of waste sulphuric acid. Synthetic resin from by- 
products of coal tar refining. 

Acid waste from purification of coal tar light oils (solvent NAPHTHA) is dissolved in aromatic 
hydrocarbon to desired sp. gr. then diluted with aq. in such quantity as to prevent too high 
temp. and resultant discoloration. The resinous soln. must be of less sp. gr. than diluted acid 
in order to separate well. 


1,429,265—Sept. 10, 1922. William AcHTMEYER, Connecticut. 


Condensation product of phenol and formaldehyde and method of making 
same. Improved thin liquid and noninflammable resin for impregnating purposes. 
PHENOL and FORMALDEHYDE are polymerized by usual process with sodium tungstate as con- 

densing agent and a neutral solvent less in amount (20-25 per cent) than the solute. Sodium 

phosphate, etc., may in part replace tungstate. Water is solvent used in illustration. Other 
materials are claimed. 


1,429,267—Sept. 19, 1922. William AcHTMEYER, Connecticut. 


Phenolic condensation product and method of making same. A non inflammable, 
insoluble, resistant friction compound. 

PHENOL and 0.75 parts methylene DIPHENYL diimin are boiled until the 5-6 per cent aq. 
formed by the reaction is expelled, then mixed with 7-10 per cent para FORMALDEHYDE or trioxy 
METHYLENE, etc., and again heated. Other materials are claimed and properties and methods 
of application as impregnating agent given. 


1,430,034—Sept. 26, 1922. Walter O. SnELLING, Pennsylvania. 


Vuleanized oil product. (Process also claimed.) Rubber with desirable cohesiveness, 
toughness, elasticity and plasticity. 

O11 is treated with sulfur chloride in excess of that required to produce vulcanization. A 
solvent (benzine, gasoline, CS,, etc.) and accelerator such as hydroxy stearic acid may be used. 
After vulcanization the product is kept at 180° in closed container until the desired degree of 
softness due to depolymerization is acquired and then action is stopped by removing excess sul- 
fur chloride by kneading or washing with ag. or alk., or blowing in air, inert gas or steam. 


1,430,538—Oct. 3, 1922. Harry H. Cutmer, Kansas. 
Hydrocarbon product and process of making same. Material for synthetic 
rubber. 


Vulcanizable products result when ozone is brought into intimate contact with OLEFIN and 
terpene hydrocarbons, heat being regulated to avoid material distillation and continued until 
substance is solid or semi solid and elastic. A wide variety of material is claimed and apparatus 


shown. 


1,435,801—Nov. 14, 1922. Alexander BLUMFELDT, Switzerland. (Basle.) 


Resin and process of making same. Phenolic sulfur resins. 

PHENOLS are heated with sulfur and a quantity of a basic substance (KHS or anilin, etc.) 
not more than o.2 of that required to neut. the phenols, using a halogen or its comps. with S, 
Se, Sb, As, Bi or other metalloid, as catalyst and if desired hardening the product in molds by 


using HEXAMETHYLENETETRAMIN or other material capable of splitting off formaldehyde. 


1,441,598—Jan. 9, 1923. 
Max Pui.iips, Wisconsin, and Gerald H. Marns, Michigan. (U. S. Gov’t.) 


Product made from furfural and process of making same. Resins for varnish 


and enamel. 
FURFURAL and 3-NITRANILIN or 1-naphthylamin, 4-toluidin, or other amin, etc., are heated 


together in presence of a halogen acid as a catalyst. 
31 


476 DIGEST OF PATENTS 


1,443,381—Jan. 30, 1923. Stanley J. Peacury, England. 

Accelerating the vulcanization of rubber and method of producing the 
same. (Product also claimed.) Nitroso dimethyl anilin and sulfur derivatives as ac- 
celerators for rubber vulcanization. 

Nitroso dimethyl ANILIN, 1 mol., mixed with 1-2 or more atomic proportions of S, 
is heated to 130-135°. Dense red fumes given off condense to YR substance and this, or the 
residual brown resin, both act in small quantity as powerful accelerators of the vulcanization 
process. Sulfur may be melted first and nitroso dimethyl anilin slowly added. Excess of sulfur 
gives a product that may be powdered while less sulfur gives a resinous product. Processes of 
vulcanization are given. 


1,455,509—May 15, 1923. Karl Rucker, Germany. (Chem. Found.) 
Method of refining mixtures of chlorides of napthalenes serving as substi- 
tutes for rosin. Removing noxious vapors in mfr. of resins from chlorides of naptha- 
lene. 
NAPHTHALENE chlor. derivs. are melted at 215° and a current of air or indifferent gases is 
sent through the molten mass to liberate injurious substances. Product of this refining method 
has same useful properties but without injurious effects. 


1,477,805—Dec. 18, 1923. Clayton W. Beprorp, Ohio. (Goodyear.) 
Accelerator for the vulcanization of caoutchouc substances. (Process also 
claimed.) Improved method of applying nitrogen sulfur accelerators. — 

The accelerator is prepared from its ingredients before adding to the rubber mix. For in- 
stance, 4.2 parts THIOCARBANILID, 2.4 parts sulfur and 34 parts ANILIN are refluxed and temp. 
gradually raised to 190° until about 6 parts gas have passed through condenser, then quickly 
distilled until 36 parts anilin have been removed and total gas loss is 9 or more parts. Temp. 
should not exceed 270°. Preparation of other accelerators claimed. 

Note 1,371,662. 


SUBGROUP (t).—TANNINS (SYNTHETIC). 


1,336,759—Apr. 13, 1920. Otto Scumipt, Germany. (Chem. Found.) 


Soluble condensation product and process of makimg it. Colorless soluble 
tanning agent from napthalene. 

NAPHTHALENE or homolog, to parts, is heated at 130-140° in 12.5 parts 98 per cent H,SO, 
to form the beta sulfo acid, soln. is then cooled to 80-90° and 4 parts FORMALDEHYDE (30 per 
cent) added in small portions keeping temp. at 60-100°. Resulting thick mass is diluted, stirred, 
and neut. by alkali. Condensation may precede sulfonation. Trioxy methylene may replace 
formaldehyde. Product is tanning agent and aids in bringing other tanning agents into soln. 
(Quebracho). 

Note 898,307. 


1,344,950—June 29, 1920. Arthur Kortzyt, New York. (R6hm.) 
Tanning material and method of producing the same. Tanning material from 
salicylic acid. 

Five parts sulfo saLicyLic acid or other phenol carbo acid are dissolved in 7.5 parts conc. 
H,SO, and at 50° one part 40 per cent FORMALDEHYDE is slowly added. By sulfonating before 
condensing the sulfo group takes the para position to OH in salicylic acid, but if condensation 
takes place first* the methylene group takes the para position and the sulfo group can only enter 
later into the ortho position to OH. The latter product tans leather a dark and the former a 


light shade. 
1,344,951—June 29, 1920. Arthur Korrzir, New York. (Rohm.) 


Tanning material and method of producing the same. Tanning material (for 
making white, soft and strong leather) from cresotinic acid. 
Process is similar to 1,344,950 using 3-CREsoL carbo acid (3-CRESOTINIC acid), 3.5 parts acid 
and 0.25 parts 40 per cent FORMALDEHYDE at 90—-100°. 


1,344,952—June 29, 1920. Arthur Kogrziet, New York. (R6éhm.) 


Tanning material and process of producing the same. Tanning material (for light 
colored strong leather) from halogen naphthalene. 


* Note 1,232,620. 


PM 9 


Lae eer 


pa 


GROUP XXIV.—FINISHED PRODUCTS OTHER THAN DYES ATT 


Process is similar to 1,344,950 using 1-chlor NAPHTHALENE or the 1.4-dichlor deriv. with 4 
iparts acid and 0.3 parts 40 per cent FORMALDEHYDE at 40° for mono chlor comp., or 4 parts 
fuming acid (20 per cent SO,) at 1oo° then o.2 parts HCHO (40 per cent) at 40°, for dichlor 
deriv. 


1,375,975—Apr. 26, 1921. Adolf Romer, Germany. (Pickhardt.) 
Manufacturing substances precipitating glue. (Product also claimed.) Tanning 
material from naphthols. 
I- OF 2-NAPHTHOL, or sulfo derivs., 1 mol., and 1-1.25 mols. conc. H,SO, are heated 4 hours 
at 120° (above 100°) or with equal parts POCI, as condensing agent at 100°. From 1-q per 
cent of product is used in tan bath. 


1,375,976—Apr. 26, 1921. Adolf Romer, Germany. (Pickhardt.) 
Manufacture of substances precipitating glue. Tanning materials from naphthalene 
sulfones. 


2.2/-DINAPHTHYL sulfone or deriv. is heated at 200° with equal parts conc. H,SO,, cooled 
and mixed with 0.12 parts FORMALDEHYDE, stirred some time and partly neut. with NaOH. 


1,399,510—Dec. 6, 1921. Willy Mortter, Germany. (Chem. Found.) 
Process of making tanning materials. Tanning agents from phlobaphenes and 
resins. 


A PHENOL deriv. of an aromatic hydrocarbon is condensed with FORMALDEHYDE in presence of 
sulfuric acid to an insol. product which is oxidized by persulfates or other to an aq. sol. or col- 
loidal tanning agent. Patent discusses colloidal conditions at length and gives 16 examples of 
processes and material used. 


1,412,949—Apr. 18, 1922, Arthur LurtrincHaus and Louis BLancey, Germany. (Badische.) 
Manufacture of soluble condensation products. (Product also claimed.) Tanning 
materials from carbohydrates, etc. 

CELLULOSE is dissolved in 15 parts 66° H,SO, and nearly 2 parts finely powd. NAPHTHALENE 
are added at not too high temp. Product is converted to lime salt then to Na salt in usual way. 
Any carbohydrate such as starch, dextrin, sugar, etc., and any aromatic comp. at least bicyclic 
and free from hydroxyl groups, such as alkyl or halogen or sulfo naphthalenes, anthracene, 
phenanthrene, carbazol, etc., may be sulfonated and condensed as above. 


1,421,701—July 4, 1922. Oscar Low-BrEer, Germany. (Chem. Found.) 
Tanning substances for tanning animal hides and process of preparing 
the same. Tanning material from mixed components. 

A CARBOHYDRATE, 2 NAPHTHOL sulfo acid and FORMALDEHYDE are condensed to a tanning ma- 
terial, the two components united by the condensing agent being different, and only one need be 
an aromatic deriv. Temp., the strength of acid and other conditions will vary, sulfuric acid need 
not be present or alk. sulfite may take its place, or P,O; be used. 


INDEXES. 


ASSIGNEE INDEX. 


This index is a key to the list of assignees in column 3 of the Patentee Index, 
and also to name of assignee in parentheses following name of patentee in each 
abstract. Addresses are given as they appear in the patents. 


Name of Assignee Address 


AbDbotl ‘Laboratories: ies ae eicva vc crore) leheretessaetanels) sieloievaimre totals + i atazy ate Chicago, Ill. 
Actiensgesellschaft fir Anilin Fabrikation. See Berlin. 

Actiensgesellschaft Kalle & Co. See Kalle. 

Actiensgesellschaft fiir Chemische Industrie. See Rheinau. 

Actiensgesellschaft Rutgers Werke. See Rutgers. 


Adam; Matthews As: cic's «eerie ecco suoeale eleielece’s Wlplawislacsle erate eiesanemele London, England. 
Aetna’ Explosives Co... Tne. F< is escsis bien ct hielo nw aie Mikiele cana et New York, N. Y. 
Albany Anilin & Chemical Works ..........cccccccccccccacecs Albany, N. Y. 
Albany Coal. Tar Dye &,Chémical Co. 22 oicsucle os oleu cis sete Albany, N. Y. 
Alien Property Custodian. See U. S. Gov’t. 
American By-Products Cos oo sdcceas conse 6 dates ecm dtarerk ters New Jersey. 
American Cellulose & Chemical Manufacturing Co. 55 nee Delaware. 
American. Dyewood! Co. ic a5 ka n's 2 uy woe cae eb le ops ie te New York, N. Y. 
American: Rubber Goi) ccs esas soc bay gla saree cralenloneeenete Massachusetts. 
American Synthetic’ Dyes.) Ines fois ics eee oie se eee ee ae Virginia. 
American’ Waterproof Cloth Co... 55 sscvene ssc thiae ote Brooklyn, N. Y. 
eelee eae & ye Works. See J. R. Geigy. 
Frno rint OTKS «6.6 c.sie% a, otal alee wie ee iee. pene a dele sia e eLlenalie wa 6 adh oye are lS 
Atlantic: Dyestuff ‘Comic, ioc ccs ec ere em sais ete tL eee engine eet oe 
Ating Powder®Go; 23 oo oekse cae #0} d:.6 '8) 01/8; ie llell anal Bite im (0 SV Gi staat a eRe Wilmington, Del. 
*Badische Anilin & Soda Fabrik .........0cccccecscrvvesvos eile : 
Bakelite :Co:, ‘Generals .05 Oooo cee pee ee eee eee sre Nannon, yopany 
Barking Chemical Co. sade ere aloes Sih awe a-bak ieitel Giga aoe eiecuie tree We London, England. 
Barrett: Co, The oo. heen. a eee Ly Seats Ae New Jersey. 
Basle, The Society of Chemical Industry of .............. ‘Wise Basle, Switzerland. 
Basle Chemical Works, Bindschedler. See Bindschedler. 
Bayer & Co., Farbenfabriken vormals Friedrich .......... stealer Elberfeld, Germany. 
Beach, ‘Edward Seo sus. een. Sabha ae ae Pe ee ohn aa Ridgefield, Conn. 
Beckers, W., Anilin & Chemical Works, Inc. .......... pote aon Brooklyn, N. Y. 
Berlin. Actiensgesellschaft fiir Anilin Fabrikation ......:.0..40 Berlin, Germany. 
Beyer & Kegel. (Leipziger Anilin Fabrik) ..........ccccccece Lindenau, Germany. z 
Bindschedler, Basle Chemical Works ..........cccccccccccece Basle, Switzerland. ras 
Bloedeé Co., Victor GG. oui s hee ns oe be caeee pee ee Baltimore, Md. ; 
Blumberg & Kindskopf) 5.7) .5.30 45 bite (seen eee Teplitz, Austria-Hungary. 
Boake, ‘Roberts & CO. 00. vue wxiselatile sacau Sens Sue ee eee London, England. : 
Boehringer ‘und Soehne, (C.F, pics oe2 ee ee eee Baden, Germany: i 
Bostaph Engineering Corp. i. 50..6.5).0h56skee cee eee fe Detroit, Mich. i 
Bourgade, (sastave os 0% 6 eias aves wa anise bel asa ae New York, N. Y. > 
Bregeat) Corporation of “America a6 sea cee eee Wilmington, Del. i 
British Alisarin’ Co Lid. f.i.%sscu le Oe on ee oe Manchester, England. 
British Dyestuffs Corp., Ltd...) 4.5.06 +0) pile elcp a uee London, England. 
Bronner, vormals Farbenfabrik Frankfort, Germany. > 
Brooke, Simpson’& Spiller iii. . Uae lek eee ee ee cue eee ee London, England. 2 
Brown, William (Morgan (i500 859. Sa eae eee London, - England. iE 
Brugge, A. G., (Chemische Fabrik, vormals Dr. Zimmermann % 
& COD Wisc esp Bieves cue m eraee b pustaeca aves ince tacts lente aire oe ae Brugg, Switzerland. Me 
Bunnell, M:. Dick sige vist whisis aces cela dina ae ale ae et San Francisco, Cal. ff 
Burtnett, Abraham Garrison 6.030.550 0s nckot soon eee Lait Bronxville, N. Y. * 
Butterworth-Judson Corp. ........eccceevees PEE i ue, ate New York, N. Y. = 
43 
Cassella & Co., Leopold ............ ahd sig pips wo Rep epee ne Frankfort, Germany, % 
and New York, N. Y. te 
Carter, Dinsmore: & Cow cin ciiseice-as swab © 4s cel balou ane Brooklyn, N. Y. ig 
Celluloid Manufacturing Co. ie. ses sic ois) sienielal see reteousivereeanee New York, N. Y. 
Chadeloid.: Chemical. (Go. 0 yim acc aw coke ais os arereeie lei cetera e ee West Virginia. 
Chanee & Hunt, Ltd. (Alfred F. Holly and Owen E. Mott.) .... Oldbury, England. 
Chemical Development Or See Ere AC A oo Augusta, Maine. 
Chemische Fabrik auf Actien, vormals E. Schering ............ Berlin Germany. 


Chemische Fabrik, vormals Sandoz. See Sandoz. 
Chemische Fabrik von Heyden Actiensgesellschaft. See won 
Heyden. 


ASSIGNEE INDEX 


Name of Assignee 


Chemische Fabrik, vormals Weiler ter Meer See Weiler. 

MEL MIO? SR SRMAM LOTT L1G. 5's. occ so ee so 0,00 clan ans ov vicnsee vows 
Chemical Products Co. 
UNE ET RMD Ot) ee eerie ol cores esha lees c a,cnerecnileje elee ale cis Vege oie og 
EE MICRO R Ces s og Kos sacri sagevigcidesecsoeruceas 
vas Asasipsalhieiny & 5 OLE aS tld oct ROC CRE Toe ae 
ne een cea tee Sale o's) oe, 5.5 aioe vie <6 bcc seas obese eciees os 
Ree ROO Ee AUT UMC EC aeye ci gie's, tis; as cio 6.6 l0cs v0 o'ee's 6% vdieo sew encase 
SearEsbeerClal Ete S@mECMM. CO. . ccc oc seen cess ce cetncccsveeseeven 
Compagnie Nationale de Matieres Colorantes ............22000- 
Compagnie Parisienne de Coleurs d’Anilin ...........0. ee eeeee 
Consolidated Color & Chemical Co. ....... cc ccctcsccacscccens 
Consortium ftir ElekKtrochemische Industrie ..............-08. 
Cordes, Hermanni & Co., Ichthyol Gesellschaft .................. 
Granmaumigde, Societa General per la ..... ccc cece cess encnencvece 


Dahl & Co., Wiilfing—, Actiensgesellschaft. ........c..ceeeceees 
(peer, UCM SRALGS so SNE Sra Ge ee 
PivermxnttOlogical Research Faboratories .......ccenccecreeccscucs 
Deutsche Gold und Silber Scheideanstalt, vormals Roessler. See 
Roessler. 

Deutsche Luxemburgische Bergwerke. See S. Hilpert. 

eee iy and tT Raynolds Co. 2... ccncsetensersevaces 
basa ten CREE Cy em ATC CIN fsec se se cc macew s 28 eos au sais wales a es.s es 
MES M AV EE Sar CM eIIICAl BMC I cc dic vis sae o o0 sc 0 cleis wisn ove e's sss eeee oe 
LUetRvcny (Ci cgkrtesil) (GG) gk ast Sa aries trea ar ae ar 
aR ROTI TINE ATU COG e sere alee sigio snc siaccc sit ocisiv cesses. de teessetows 
Ulver nt, TRyesivece De sveeS. 5 eee Gio ae DOICEeL ona ROR MRI eee 
peepee oe Nemours w Co. WH. Dy ow. cee tee veces ecsvinnes 
Durand, Huguenin & Co., Dyeworks formerly ..............5008- 


PPE AIASU OR MICO CALC Olt tiie a releis. 3 oe sls 6.04 44> 400 60 6 0 0% 6 ose ws aiers oe 
RORECE SME Niatiitactiring CO. avis ccc tcc ese sec te ce eee nea wae ce 
Elberfeld Co., Farbenfabriken von, (see Bayer.) .......... 
aa ORR CMO Ns siege silat wes we oes ces esse sues be cow ace sienile 


eeceerer eee eee eee eee reese eeeeseseseeeeeoeseeneos 


Fabrik Chemische Praperate, von Dr. Richard Sthamer. See 
Sthamer. 

Fabric Ormnamenting & Manufacturing Co. ........-.eeeeeeeees 

Fabriques de Produits Chimiques de Thann u. Mulhouse. See 
ULER SN SRN lei iGrs ac aaie soso gics lewis kets 64s bin ere see a ae 8 8 80 

Farbenfabriken, volmals Friedrich Bayer & Co. See Bayer. 

Farbfabrik, vormals Broénner. See Brénner. 

Farbenfabriken von Elberfeld Co. See Elberfeld. 

Farbwerk Miihlheim, vormals A. Leonhardt & Co., See Leon- 
hardt. 

UME EPCS E Witt, FIANMTON foe ee ce ee tee eset sede veces nesus 

NRC NM OCG) PTBNL Sac cic ewe ce reece rene ne esc arwese nes 

eee Bee was 20) SEE oe crc e ails ot 6) S216. oc s.01c.2 06.6 wiecieiene eo Wise 96.6 eles 6 eaislias 


Seem Licht & Cake Co. ... cnc cece sence cccscesesesngescevevens 
GesOlimne Recovery Corp, 2.2... ccc cc ccc cc ccc esccescccscces 
BRMROMMG WV TIATN ING occ cc ct cect cee ec eceee rs eenseteresetas 
Geigy, John R. Anilin Color & Extract Works ..........eeeeeees 
Wremeral Omemical Co. ....52.-. 00 c ecco cccces ae pub he in otiie 
General Motors Research Corp. ........ccceccccececerevsceece 
MRPUBOM gs FUUS oon ss ee cen eens ccc ees enrtocsceseneess fees 
Gilliard P. Monnet et Cartier, La Societe Chimiques des Usines 
du Rhone. See Soc. Chim. 


MEORERIIMTE So SPCHCEF 2. www cc ecw ce cr rem ce encsresecesennvuces 
Gold und Silber Scheideanstalt, vorm. Roessler, sche. See 
Roessler. 
Goodyear Tire & Rubber Co. .... cc ccc cece eee e cere e eres eeens 
Geeemells Chemical Co. ccc sce ccc ce cc nee teense ae sinevsseenic 
Griesheim-Elektron, Chemische Fabrik ..........eeeeeeeeeeeees 
Grunau, Landshoff & Meyer, Chemische Fabrik Aktiengesellschaff 
Hansmann & Co....... A RO A SF Eee oe TOE ONE on Ce 
NE ee ee hice ard bec ben ese co Were NOs gem ades sem sare oe 
PPRRPURIOM Se POWUCE CO.) occ ceed sciasc@awe ees e590 606.6 o¢ 90is0.9 6.01018 
Heydem Chemical Co. .......ccccee cece see rccreseccereacs er 
Hilpert, S. Deutsch Luxemburgische Bergwerk und Hutten 
Alctiengesellschaft 22.2... 2.2 ccccccccntccesenencceeneesornces 


Hoehst, Meister, Lucius & Brtiming .... ee ee eee eee ee sere eeees 


479 
Address 


Delaware. 

Boston, Mass. 
Manchester, England. 
Clayton, England. 
Barmen, Germany. 
Arkansas. 

Sandusky, Ohio. 
New York, N. Y. 
Paris, France. 

Creil, France. 
Newark, N. J. 
Nuremberg, Germany. 
Hamburg, Germany. 
Rome, Italy. 


Berlin, Germany. 
St. Petersburg, Russia. 
Philadelphia, Pa. 


New York, N. Y. 
New York, N. Y. 
New York, N. Y. 
Wilmington, Del. 
Midland, Mich. 

Boston, Mass. 

Wilmington, Del. 
St. Fons, France. 


Rochester, N. Y. 
Philadelphia, Pa. 
New York, N. Y. 
New Jersey. 
Berlin, Germany. 


New York, N. Y. 


Thann, Germany. 


Basle, Switzerland. 
Hamburg, Germany. 
New York, N. Y. 


London, England. 
Wilmington, Del. 
Indianapolis, Ind. 
Basle, Switzerland. 
New York, N. Y. 
Dayton, Ohio. 

New York, N. Y. 


London, England. 


Akron, Ohio. 
Cleveland, Ohio. 
Frankfort, Germany. 
Griinau, Germany. 


Vienna, Austria Hungary. 
Feuerbach, Germany. 
Wilmington, Del. 

New York, N. Y. 


Bochum, Germany. 
Hochst, Germany. 


480 DIGEST OF PATENTS 


Name of Assignee 


Eo ti mam 6@ Kaiessig 5 eis eaece. oe eevee cats Dn ee Oe ae + ete 
Hoffmann-La Roche Chem. Works. See La Roche ............ 
Holley, Alfred EK. and Owen E. Mott. See Chamce .............. 


Hollidgry; oh Bish Comm aie tee ns isen s cheile Wicks ister e Gist ete chee eee 
Holliday & Sons, Ltd. Read- See Read-Holliday. 

HookerElectrochemical "Cos ve s% sc ne uc cisco etenateere letersi eeneeeeete 
Hoops, Urs Henry W.e.ie we occa fctsis toe kee lolere occa eleva eis eerste 
Horowitz, Arthur ioe ec Felice 2 osticrcieie oo oelece oe ale ntaleis evereter ieee nee 
Huamt, Seth. cB. Get aicecic «| grit bisseieaie ori pinie sate el ete severe eee Ree ee 


Ichthyol Gesellschaft, Cordes, Hermanni & Co. See Cordes. 
Imperial Trust for the Encouragement of Scientific and Industrial 


eoeeveeceee 


RESGALGH. Vilace.sisidinyaighe.o-o t sveisie es Bivial ounces wisrersvarteelaeletebel tT Shehene ne Renee 
Import. & By=Products; Co. : tic cas + wets slecere tsite es sian et eaee eee 
Industrial Alcohol Co., U. S. See U. S. Ind. Ale. 
international) Coal (Products (Coss:2.5.. 6 eet ee ec eee eee 
PAREOE, Carl uss 55 occcécate haile ctereeier ete. oe: a oie eave tetas leetaroneve ten ue Renee 
KK... & -P.: Chemical | Corpic ic so vei cage nie © cesta wie) tue oes sient er a eee ae 
Kalles& Co., Aktiengesellsclatty ics ci. srerereusic cna lenlv eters teri etel enna 
Kalmus; Comstock & Wescott, Ince savas ss ca cies co eleieina seen 
Karerag, Patil op siiiecacis s clcteveeisis svete sities cvsie ene sue eal este) eaten a een 
Weller, Job) eon. co cio coo oo lece wie guest alle a) eineifele mie cle er eeetel tein aman 
Kellogg, Marie Loutse .cis0 ve ss eos ee © ore € shel ices aoa 
Kinzleberwer & oo. i. 6ag vuieie be actos bik nlele ole aleleerelaiercie eae eae 
KH pstein’ & Co. se. a re Se ls tenet cn eee 
Klimoseh,” Konrad Pdward sik, cys wesc osne aietee’e een ele nonin temas 
FRM OL & COs ee oe oes sevee pia tee oe terciare mice aay Rone ciel slerelee ry att ee 
Moppers (Co., The i. cece bic ies are hoes 8 aiecel e eete leit cae slated teres 
Kuchler’ & Butlin eulecs i ve cece wees eine 6+ wielacs oO alscciecs en ieee 
Kuttroff-Pickhardt & Co See Pickhardt. 

Lambert, Jr. Jean, and Chas. Rumpff (27-7... <1 -icisls olen teu 
Lapperr, Nathan Sos ii. oc ceo vce ts cuniy or atee cic eapeteiele Ste eee eneeeae 
La Roehe Chemical Works, Hoffmann- .........0..s+00+eeese> 
Laundry Bltre@ Cos iiss dice wicvovecnieicis a siu s heatiele etait ae eee 
Leeds: Manufacturing: Cos sins cc s/c alee )e lets nities aiatoys, comeleiettieaeteteieeninee 
Leipziger Anilin Fabrik. See Beyer & Kegel. 

Lembaceh, Adolf, Ulrich Schlicher and C. F. Wolff ............ 
Leonhardt & Co., Farbwerke Miihlheim, vormals .............. 
Levinstein. Co. [td., ‘The? oo. case cteistete 6's. la's)s nels aie ele cee 
LiZhtloots Job Pe. eee ce eiacsvaleuvle sue 4 arp) eos aren Shean ealng tote ne ae een en 
LAM y 8 Cor esate ee on ere erst care sine ete: bias bana oan oe ke 
List, Adolph? oy i Pele cies oes arenes tlale sll sis are ae sacle ene Onis ace ee 
Lonza,) ‘Blektrizitatswerk, , 2)... 5.0/0 stso'e 1 as elie slalots se ivi corona: saslene amen 
Macdonald, David Baird © isis vis alevs crs iole  copele tise ere eerie 
Macdonald, Luachlan: Wa. ... v.05 vc ola cielo e oieronsleletn ele rele tetenaerntte nae 
McKee; Ralph od ieee wie 5 case eie eles te loo deeerta otis cette eee tetera ie eee eee 
Martinon, Barthelemy. ii) s sis 6 «0 415 Sleie a eles e oll e tials ete tsiereiy ten eanme 
Mather,’ Carl Noviuics. cre nua-stetictene marae oe tar eteheuetpstetetoaoteestene is oleaetese estes 
Matheson & Co., William Jo. o's. io. 6 iean 0 ote wis eb ele Saree 
Meister, Lucius and Brtining. See Hochst. 

Mlerelks: Fi 251 ooo sae w 6 econ gia ie vlere Sie eho elie! lets] elie rateuarss aus i teas ame 
Merrimac ‘Chemical (Cosi o0 succes wicca tiers) ie) olecele aie) oaleie sip icnet eee 
Merz, Kaard so. a as oes kG) iow coh ws Sree aie iene ete te ere 
Metalite Con Pardes Giee ee be Coie era ane ie che teeter ste eee 
Metz, Herman) As oiciic cic ie es tee eine o gin ee releieiti lene east ain anemone een 
Mitsui Mining (Cos (...\si ais os oo oenie pis se a a hiv nisl ate wade ee sive ee 
Monnet et Cie, Societe P. See Soeiete Chimique ............. 
Monsanto’ Chemical Works) 5. 7. 05 sienere wie pisiteveis e eiste eerie 
Morris, Edward (S.0 2h osc encase cle sce baw eee ete eee ene 
Mounsey, William. Edward 0.4.05... ss .cate ce eee eee 
Miuhlheim, vorm. A. Leonhardt & Co., Farbewerk See Leonhardt. 
Miiller-Jacobs, Catharina, & August Loos ............2.e0ee00- 
Mitlier-Pack, J J. vdkcs'ce va cseisns woh s biplalere ss otela Serenent a eres naene 
National Anilin & Chemical Co., Ine... oe ee oe eee tenet 
Oehler, Ke Fe. coed wile «cts Crete sete grace tele oe th ele ttetere he eete eee ana 
Parke, Davis & Co. (...66%8 cabs eckaivee oven ee eee een 
Parsisse, Societe Chimique de lg Grande ..........ccececccececs 
Pereira; Hansii sos nieces si ose h ow levee rotten luse leone lets tehette ele: tenetete nent etme ennms 


Address 


New York, N. Y. 
Oldbury, England. 


Huddersfield, England. 


Buffalo, N. Y. 
Jersey City, N. J. 
Berlin, Germany. 
New York, N. Y. 


Westminster, England. 
Trenton, N. J. 


Richmond, Va. 
Dusseldorf, Germany. 


New York, N. Y. 
Biebrich, Germany. 
Boston, Mass. 
Szolnok, Aus. Hung. 
New York, N. Y. 
New York, N. Y. 


Prague, Czecho-Slovakia. 


East Orange, N. J. 


Vienna, Austria Hungary. 
Ludwigshafen, Germany. 


Pittsburgh, Pa. 
Crefeld, Germany. 


New York, N. Y. 
Chicago, III. 

New York, N. Y. 
Illinois. 

Brooklyn, N. Y. 


Wiesbaden, Germany. 
Mihlheim, Germany. 
Manchester, England. 
London, England. 
Indianapolis, Ind. 
Leipsic, Germany. 
Gampel, Switzerland. 


Leicester, England. 


Isle of Skye, Scotland. 


Ridgefield Park, N. J. 
Lyons, France. 

Grand Rapids, Mich. 
Brooklyn, N. Y. 


Darmstadt, Germany. 
North Woburn, Mass. 
Frankfort, Germany. 
Amesbury, Mass. 
Brooklyn, N. Y. 
Tokyo, Japan. 

St. Fons, France. 

St. Louis, Missouri. 
Philadelphia, Pa 
Liverpool, England. 


New York, N. Y. 
Burnley, England. 


New York, N. Y. 
Offenbach, Germany. 


Detroit, Mich. 
Paris, France. 
Vienna, Austria. 


aes 


Sela NL are 


Se? ina ke a 


ate ae 


: 
» 4 


dite te ae 


ASSIGNEE INDEX 


481 


Name of Assignee 


Pe  WOAESCAIDS. (ie (Olas, NICE 1 ans (an 
EMER TE MOCO IS TRIRICEE ON coe pas eee ew swe nev reed nr aaeenennne 
BasmeeEEMED s OPRIS EE MON CTHIGAIY COP co ics co scsicc cs rissaiserceeconsseseess 
ROM LICE PE TATICOIS | 62. oe cc cece cece ese rcsccesrenesecees 
Posselt, Ernest, and Rudolf Peters. See Posselt & Co. 

Posselt & Co., E. 
Ponltene Freres, Les Establissements ............ ccc cceescccees 


SALE TV SMV CTO eels cis oleieke ccs oor. oe. sis eels Sind eldiwiele sade aaleiee 
Rasechig, Frederick 
Sac Ro! Goh i a ee rr 
RMP RTOS ORCL WE SONS LGW, cats sip cicieleig sles i cies sea sigeseieesse ee 
ipemmnanoel Chemical Products Co. wis eeccsccciwaicsccccccaivins 
Reilly, Peter C. 
meemewesekts Poward Sabine (Trustee) 2.2.00. .ccccccesccsccvcece 
Rheinau, Actien-Gesellschaft fur Chemische Industrie. .......... 
NEES RUMP GPIPSY iviaviris sa as cles ecco nen sinccsce re nnds res sencews 
PMRRSEAMEVENMRGE CECH CO Gee ian csc ce Sas gos 81es 6 2.0 ace nie wars eles ewes 
Rockefeller Institute for Medical Research ............eeeeee- 
eee RESTREAME ABT CRE Rr ree ccle os ois yokes weci elie ae gasegeta@ee sae 
Roessler & Hasslacher Chem. Co. ............0ccccccccccerces 
Roessler, vorm. Deutsche Gold und Silber Scheideanstalt ....... 
Doo leis (CSV ah 22 4 5 Di Gry Sy ieee Oe Ore RcnC enn ReneS ne Ir RnR ROR ac rae ar ec 
Rotman, D. R. 
RCN eM ATO Oceans = 6% ale $16.6 winis) cle 0s sieig bo ee we edie oweieee 
Rutgers Werke-Actiengesellschaft .........cceecceeeeeescrcoens 


St. Denis Societe Anonyme des Matieres Colorantes et Produits 
MRA Say ale see cach hrc c cee censseyeece nes deervcees 
Sanderson, R. E. B. 
Sandoz, Chemische Fabrik vormals ........-0ceeeeeere rene eeees 
ERE PC ee cess ca es ese secre see cce scot se tne serene 
Scheideanstalt, vorm. Roessler, Deutsche Gold und Silber. See 
Roessler. 
Schering, E., Chemische Fabrik auf Actien, vormals. See Chem. 
Fab. 
Meee EN TERTER@ DoT COU ae ccc ccs cc ete pws we cence ne cneeeesesennsne 
GSehloepfer, Wenner & Co. ......sceceewr creer eres ere sector eaes 
Schoelikopf, Jr. Jacob F., and C. P. Hugo. See National 
Schoellkopf, Hartford & Hanna Co. See National. 
Schoellkopf, Anilin & Chemical Co See National. 
Schweitzer, Hugo, and E. N. Dickerson .......-.e+ eee eeeeeee 
Schweiz Serum-und-Impfinstitut. 
Seottish Dyes, Ltd. .........-. ccc creer cccrcccscccccecesesees 
Selden Company, The ........cccceececcerece rece cecessereeeces 
BIPIRI@TOSOLWIY COl es cc ccc ccc ect ewe ses es seers nresasenss 
Shawinigan Laboratories, Ltd. ...... cece cece cere e crew erence 
Slater, John W. and Howard Richmond ........-+eeeeeeeeerees 
Societe Anglo Franeaise des Parfums Perfectionnes .......... 
Societe Anonyme des Matieres Colorantes et Produits Chimiques de 
St. Denis. See St. Denis. it 
Societe Chimique des Usines Du Rhone, La- (Gilliard P. Monnet 


REE Eee etelale 470) 4) 6) 670 Ke) we8 8b Se OKOs S186 ©1686 6 ee) e100) 8) 0:19 B81 Be 


eee se eo eee eee eee se eee eres reese essere eee ee ee eeeees 


eoceoeer roe er eee eee eee eee eee essere seeeeeseseeonseos 


eee ewe eee eee see eee woe eee eee ereseseese ere ee sere eeese 


eee ece oe ese ee ee eee ee ees eee eee ese eee esses esesre eee 


eoebe eres oeee sees nvvovreeeeereneeaeereeseeeren 


oeoeeererese eee eere ere eee eer eee ee 


Peritetree late. aisle 64 i ie ee rrcke hce ee aio yoke ip eseiene) ae: 6, 9, sc'eleoue 
Societe Anonyme VAirliquide .......... cece cere ee eee ee eees 
Societe Generale per la Cianamide. See Cyanamide. 

Society of Chemical Industry, The, See Basle. 

Societe Chimique de La Grande Parsisse See Parsisse. 

South Metropolitan GAS Co. 2... cece cece cee treet eee eee eeeneee 
Squibb & Sons, E. R 
StaMGArd Oil Co. 6... ccc cece cas ce cc crressrrcctansersseruerses 
Stearns & Co., Frederick ....... cece e reece cree ce eet ereecseces 
Stewart, Isabella Jessie 
Sthamer, Fabrik Chemische Praparate, von Dr. Richard,......-.-. 
Btolces, John Stogdell ..... 22.22. cece rece ese resets ecsecenrces 
Sunbeam Chemical Co. .....ceceecccccerserscrecrersesreceees 
Synthetic Hydrocarbon Co. 2... cece reece cece reer ere ecceeeees 
Synthetic Patents Co., Inc. 2.0... eee e eee eee eee e ence eee eeecees 


Tainan Seito Kabushiki Kaisha ...........-.- ste e nec ceeceenes 
Thann & Mulhouse. Fabriques de Produits Chimiques .......- 


Twitehell Process Co. ....ccc cece cee c cere eee eeeeceeseererere 


Union Carbide Co. ..........+-5- Tee ne aaay teem Tien aa els: stahesetsueemone ke 
U. S. Gow’t. (United States Government) ....-..eeeeeeeeeeres 
U. S. Industrial Ale@ohol Co. .... cece ee eee eee eee eee eeeenes 


ERGERLE Shs elieim © el S48 8) .e:.6 61818 8. 0a 52) SFO SSSle ONO S RNAs Ry Ree 


Sip (6 ToL adel ee eee 6) Sh: PST CBS, WSR AO Re OO) Oe eS Bh Ie 


Address 


Basle, Switzerland. 
New York, N. A 
Point Loma, California. 
Paris, France. 


Bradford, England. 
Paris, France. 


Hamburg, Germany. 
Ludwigshafen, Germany. 
New York, N. Y. 
Tumbridge, England. 
Chicago, IIl 
Indianapelis, Ind. 
News .York, | N. 0 Ys 
Mannheim, Germany. 
Charleston, West Va. 
New York, N. Y. 
New York, N. Y. 
Darmstadt, Germany. 
New York, N. Y. 
Frankfort, Germany. 
Hochst, Germany. 
New. York, N. Y 
New Jersey. 

Berlin, Germany. 


Paris, France. 
New York, N. Y. 
Basle, Switzerland. 
Alton, Ill. 


Leipzig, Germany. 
Fratte di Salerno, Italy. 


News Work, (Nea Ys 
Berne, Switzerland. 
Carlisle, England. 
Pittsburgh, Pa. 
Syracuse, N. Y. 
Montreal, Canada. 
Providence, R. I. 
Courbevoie, France. 


Lyons, France. 


Paris, France. 
Paris, France. 


London, England. 
New York, N. Y. 
Indiana. 

Detroit, Mich. 
Victoria, Australia. 
Hamburg, Germany. 
Philadelphia, Pa. 
Chicago, Ill. 
Pittsburgh, Pa. 
New) York, (Nveys« 


Tokyo, Japan. 
Thann, Germany. 
Cincinnati, Ohio. 


New York, N. Y. 


Washington, D. C. 
Baltimore, Md. 


482 DIGEST OF PATENTS 


Name of Assignee 


von Heyden, Actiensgesellschaft Chemische Fabrik (von Heyden 
Nacthfolgers ® Dri, TH) a sisniie care oie faletaie paeate ante siela aielatn sun taco eee 


Wedekind sR S&S Gorrie e 8 cas Siac tebistele sy che boas, thanets ay deep enataente 
Weiler -ter-Meer. Chimesche Fabriken vormals ................ 
Westfalischanhaltische Sprengstoff-Aktiengesellschaft. ......... 
W. Va. Pulp (West Virginia Pulp & Paper Co.) ........000200- 
Williamsburg Chemical, Co., Une. ecco oe bisminie ne 6 sense sage 
(Wise, Morris, and, Louis Stettawer 2. cdisis «pe wine suaeiens nl enednsee teers 
IW eel fi mess} oan ASS hays ele dew clase sen wins we Wise eats ota) eleloieie la euenetche rene tas Rees 
Wilfing, Dahl & Co., Actiengesellschaft. See Dahl. 


MOUM yt CO, a eake ea eran ere ie iets tere Savevstaepapetetevote ce shetrid eaters 


Zimmer, Georg) Carle cick son ole sbeleelacers oleieres ine: sree seltteis teas Rees 

Zimmermann & Co., Chemische Fabrik, A. G. Brugg, vormals, Dr. 
See Brugge. 

Zimmermann, Emil and Chas. Rumpff ............. cece ewes 


Address 


Dresden, Germany. 


Uerdingen, Germany. 
Uerdingen, Germany. 
Berlin, Germany. 
New York, N. Y. 
Brooklyn, N. Y. 
New York, N. Y. 
Berlin, Germany. 


Hanover, Pa. 


Mannheim, Germany. 


New York, N. Y. 


ar oe 


COLOR INDEX. 


Patent numbers are here arranged by color on fiber, by method of application, 
and numerically by chemical groups. The method of application of each color is 
shown in bold-faced type, and the chemical groups are indicated by means of 


eo 


roman numerals. 


BLACK 
Acid 843,077 749,913 Basic 525,245 790,363 Ws 
843,137 753,057 Mordant 525,626 790,364 
VI. 843,149 754,264 530,532 797,441 354,746 
843,756 750,571 V. 536,878 803,592 396,293 
454,045 843,808 787,824 536,879 807,422 412,440 
456,627 844,814 790,079 536,626 555,359 823,793 425,885 
456,897 863,290 806,053 556,298 835,539 438,438 
476,336 874,967 VE. 556,439 839,489 440,639 
515,339 887,348 1,032,433 557439 843,137 449,629 
543,747 899,171 536,626 578,580 843,149 ALE 
546,068 906,421 Developed 582,958 844,814 462,415 
546,069 912,356 VI. 582,959 863 290 466,202 
557.440 921,239 II. 583,439 887,348 ieee 
562,200 Re. 13,122 458,283 583,634 nas or tage 
583,439 932,812 476,336 38,589 586,865 12,356 482,106 
593,790 932,813 502,368 Re. 4,746 588,181 es So ees 
602,856 935,031 546,070 Re. 4,747 588,182 eeaee ery 
603,093 944,328 557,440 79,942 588,203 S703 $136 
606,438 945,780 562,200 Re. 3,103 601,033 oe 045 ne 9 
611,112 950,405 628,721 96,242 602,856 9 9,450 498,772 
613,638 958,830 631,089 106,616 602,857 1,000,600 49 773 
613,639 958,912 640,010 111,654 603,008 1,014,039 501,11 
618,963 982,952 644,234 127,103 603,093 1,014,633 501,500 
624,256 982,953 654,065 138,155 608,999 1,042,356 502,912 
627,783 989,000 655,529 193,158 613,641 1,056,493 511,688 
628,025 989,001 740,767 213,907 613,642 1,078,925 512,167 
634,009 1,014,039 > 740,768 248,934 620,574 1,078,926 515,339 
639,041 1,078,925 749,195 283,220 624,256 1,092,842 516,604 
644,240 1,128,813 792,032 287,112 625,198 1,101,739 524,665 
644,334 1,128,814 792,033 331,777 627,783 1,122,564 525,245 
646,711 1,159,375 797,441 343,793 629,748 1,128,813 525,626 
654,065 1,199,233 835,539 355,934 632,503 1,159,375 526,763 
654,167 1,213,075 839,489 387,094 634,824 1,199,233 533,463 
654,168 1,235,253 841,371 390,842 644,233 1,206,232 533,508 
655,529 1,323,285 843,077 391,315 644,235 1,209,154 536,431 
664,955 1,325,841 843,149 409,819 644,236 1,213,075 536,532 
667,935 1,375,701 843,756 409,820 644,237 1,215,359 536,878 
677,231 1,408,296 863,290 409,821 644,238 1,241,153 536,879 
680,283 887,348 409,822 644,239 1,323,285 $41,750 
688,647 XV. 924,231 409,823 644,230 1,328,841 542,073 
716,242 933,841 452,324 664,955 1,363,886 $43,212 
716,289 594,106 933,842 491,673 665,696 1,365,040 543,748 
722,715 609,327 935,031 491,951 676,494 Payee 556,164 
722,716 646,795 958,774 491,961 677,231 are yet 556,208 
25,848 749,913 958,912 499,410 680,283 pees 
a pe 1,375,701 5572435 
726,695 756,571 999,558 499,088 683,120 1.473.488 E4437 
727,963 953,008 1,014,039 £29,499 692,675 Dies G8: 537,430 
727,964 1,078,925 £39,550 692,676 ae a 560,448 
727,965 XVIII. 1,233,433 §42,04€ 693,670 XIV Are 
727,966 1,325,841 592,022 716,242 . meee 
727,967 980,251 1,375,701 Re. 11,647 722,715 ees 
728,021 999,028 1,408,296 787,221 722,716 455,952 oe 
729,601 959,516 725,348 ne ene 
737,967 Acid XV. 963,056 726,695 XV. aie 
741,936 Mordant 1,105,554 727,962 $7095 Ss 
765,581 661,438 1,144,181 727,963 639,806 57855 
778,476 III. 1,144,325 727,964 675,585 ee 
790,363 XVIII. 727,965 a eed 
792,032 368,054 Il. 727,966 XVIII. et a8 
792,034 . 450,037 999,028 727,967 Ate 
7975441 452,210 646,795 729,001 980,251 soe tas 
797,731 599,425 Basic 737,967 - sean 
797,732 619,114 VI. 741,936 Direct apnas 
803,592 623,638 VI. 759,613 200) : 
823,793 631,613 473,928 765,581 Ill 591,61 
835,539 631,614 1,028,140 493,564 770,177 . 594,996 
839,489 646,795 1,029,639 501,160 778,476 595,021 
841,371 653,492 1,032,433 501,500 778,610 653,492 599,532 


484 


DIGEST OF PATENTS 


BLACK—(Continued ) 


601,033 683,120 1,092,842 102,270 Re. 11,659 646,873 764,734 

602,856 688,478 1,099,676 1,079,568 532,484 647,493 901,970 

602,857 692,675 1,101,739 1,261,858 532,503 647,846 904,224 

603,008 692,676 1,209,154 1,464,079 545,337 648,597 909,155 

605,103 693,670 1,215,359 546,576 648,753 927,868 

608,999 717,550 1,235,253 VII. 560,334 648,754 935,009 

613,641 748,076 1,241,153 594,105 648,755 961,387 

613,642 759,613 1,363,886 872,086 594,106 649,218 961,388 

613,645 770,177 1,365,040 881,157 594,107 650,293 1,026,881 

615,47 778,610 1,371,979 941,152 596,559 650,326 1,099,039 

618,963 807,422 1,3725439 947,030 597,983 650,327 1,105,515 

61y,194 832,393 1,378,388 985,767 601,363 651,077 1,151,628 

619,503 585,444 1,415,704 985,768 601,365 651,122 1,187,614 

620,574 859,930 XIV 985,769 608,355 653,277 1,261,394 

629,748 950,404 : 985,770 609,327 653,278 1,265,837 

634,009 963,739 455,052 1,001,457 610,541 655,659 1,274,351 

634,824 969,450 { 1,005,140 618,152 661,438 1,279,307 

hoe 982,952 XV. 1,005,141 Sepp 665,547 1,316,742 

39,041 987,417 1,144,577 26,897 

644,233 999,558 546,576 1,157,485 628,607 aap ee! Stole 
629,221 71,90 

644,235 999,713 9» 1,243,170 628,608 peer 

644,237 1,000,606 639,806 1,466,687 628,609 ie Lakes 

644,238 1,014,633 647,846 629,221 ay 2 

644,239 1,014,982 647,847 XV. 635,168 San 

644,291 648,753 : 692,174 VI. 

644, 9 1,014,983 Baers ; 635,169 695,835 

eee es 1,014,984 667,689 ae 636,066 698,220 

ioe 1,028,140 : 639,806 701,051 953,008 

665,696 1,028,306 aati Sulfide Vat 641,587 702,369 

671,543 1,029,639 641,588 706,969 XV. 

673,079 1,056,493 Lid, mV. 641,589 711,038 

676,494 1,067,881 644,059 740,465 

679,221 1,078,926 975,863 523,138 645,738 764,733 1,206,232 

BLUE 


I 


Acid 
Til. 


5955349 
5955350 
605,508 
605,921 
617,981 
623,219 
623,220 
632,621 
648,271 
648,332 
654,294 
656,668 
656,669 
656,670 
656,730 
658,513 
658,514 
666,594 
666,702 
668,445 
669,894 
673,691 
675,572 
675,574 
675,575 
682,523 
687,658 
688,645 
692,762 
704,798 
7075373 
707,374 
71 1,31 16) 
713,432 


715,062 
727,389 
729,073 
734,866 
738,614 
738,375 
754,768 
764,837 
779,825 
831,002 
844,835 
958,850 
1,045,805 
1,078,505 
TIT, 510 
1,207,981 
1,280,648 


V. 


451,502 
524,677 
602,544 
603,013 
606,295 
609,352 
673,640 
872,815 
940,354 
1,015,354 


VI. 


345,901 
3575274 
454,645 
456,807 
502,369 


521,985 
521,986 
524,009 
524,677 
531,977 
534,809 
539,699 
546,068 
5573438 
563,383 
563,384 
567,615 
611,664 
633,639 
634,009 
652,456 
654,064 
677,227 
677,228 
677,229 
677,230 
700,565 
703,105 
710,059 
718,181 
722,860 
727,962 
727,964 
727,966 
727,967 
739,118 
741,552 
754,315 
759,284 
7973441 
797,461 
798,808 
805,918 


806,415 
826,279 
826,280 
826,281 
826,282 
827,468 
841,371 
843,077 
843,137 
843,149 
843,808 
844,814 
846,511 
865,252 
877,643 
879,053 
891,931 
921,105 
921,105 
Xe. 13,121 
032,812 
932,813 
958,830 
1,014,039 
1,023,199 
1,024,308 
1,028,006 
1,052,262 
1,128,813 
1,128,814 
1,188,421 
1,216,760 
I,235,253 
1,316,781 
1,323,285 
1,325,841 
1,375,701 


1,402,350 
1,429,781 


VII. 


524,256 
540,564 
620,442 
621,652 
622,139 
677,239 
677,240 


XI. 


348,816 
444,538 
451,502 
531,148 
534,809 
547,173 
585,934 
643,338 


XV. 


594,106 
609,327 
953,008 


XVI. 


434,493 
607,408 


XVIII. 


297,416 


331,964 
331,965 
333,861 
412,615 
422,018 
437,989 
463,898 
472,091 
490,408 
506,918 
519,971 
538,215 
547,173 


564,801 


567,567 
580,186 
580,187 
580,188 
583,267 


603,016 . 


605,119 
621,393 
647,260 
647,834 
658,504 
668,580 
673,632 
676,555 
680,732 
688,066 
709,160 
727,964 
835,682 
877,052 
887,620 
891,888 
891,889 
976,417 


978,801 
9955494 
998,139 
1,026,089 
1,042,498 
1,052,262 
1,065,405 


Re. 13,969 


1,277,238 
1,237,192 
1,387,596 
1,478,039 


XIX. 


413,049 
551,885 
1,054,247 


Acid 
Mordant 


iit, 


258,530 
399,480 
399,481 
399,482 
401,633 
401,635 
446,892 
476,418 
476,419 
476,420 
496,139 
502,603 
502,765 
503,295 


a 


506,265 
519,229 
527,457 
569,418 
569,419 
595,349 
5951350 
605,568 
605,921 
617,686 
617,981 
619,115 
623,219 
623,220 
627,896 
631,613 
631,614 
632,621 
633,950 
648,271 
648,331 
648,332 
653,492 
654,294 
654,505 
654,506 
656,668 
656,669 
656,670 
656,730 
666,594 
666,702 
668,445 
673,691 
675,572 
675,574 
675,575 
707,373 
707,374 
729,073 
734,866 
738,614 
748,375 
753,057 
754,264 
754,768 
779,825 
868,399 


1,090,123 
V. 

536,626 
VI. 


420,372 
420,374 
447,302 
502,369 
654,064 
683,119 
684,065 
718,028 
749,195 
797,441 
805,918 
806,415 
826,279 
826,280 
826,281 
826,282 
827,468 
841,371 
843,077 
843,137 
843,149 


846,511 

865,252 

999,558 
1,014,039 
1,025,267 
1,114,771 
1,221,849 
1,233,433 
1,234,094 
1,237,192 
1,237,193 
1,259,499 
1,203,231 
1,292,385 
1,316,781 
1,323,285 
1,325,841 
1,375,701 
1,408,297 
1,419,501 
1,426,189 
1,426,190 
1,431,655 
1,437,758 


VIII. 
617,628 
XI. 


252,274 
253,443 
253,444 
253.445 
255,350 
364,320 
366,356 
366,357 
420,164 
440,536 
444,532 
497,114 
518,458 
524,235 
531,148 
534,809 
547,173 
585,934 
613,578 
616,622 
638,576 
643,338 
662,224 
707,832 
707,833 
807,181 
842,303 
844,156 
893,855 
895,635 
898,039 
898,098 
898,842 
902,154 
936,247 
955,040 
961,362 
992,613 
1,000,899 
1,028,045 
1,199,458 
1,227,407 
1,268,455 
1,299,070 


COLOR INDEX 


BLUE—(Continued ) 
XV. Basic VI. 
Mordant 
657,768 447,302 
657,769 V. 501,500 
525,492 
XVI. 352,361 536,532 
392,723 556,298 
323,514 458,281 558,344 
332,514 491,378 558,438 
469,329 511,653 569,392 
524,322 536,626 578,432 
520333 617,703 578,580 
536,163 566,162 
539,738 VI. 588,203 
560,795 601,033 
606,212 524,251 oo 
524,252 602,85 
XVIII. 524,253 611,597 
524,254 613,641 
331,964 613,642 
333,861 Da, 614,391 
478,005 629,748 
484,697 254,064 644,233 
538,215 254,065 644,238 
377,052 255,349 pbs 
877,053 369,764 676,495 
877,054 404,309 677,227 
976,417 413,562 677,228 
998,139 431,541 677,229 
1,004,610 442,680 677,230 
1,042,498 494,838 692,675 
1,044,836 400,243 710,059 
1,065,405 1,188,259 718,028 
Re. 13,069 eee 
T2375. 727,904 
37> 93 XVI. 727,966 
27,96 
XIX | sogirgs | 7270902 
1,88 eaeneT 797441 
Pik 380 270,311 806,415 
2194;3 362,502 ee 
Basic 366,639 843,137 
366,640 g 
43,149 
V. gues 844,814 
905! 
393,300 oh ae one 
456,201 2 
1,378 879,053 
ee XVIII. 888,030 
578,003 916,323 
613,920 263,420 920,151 
726,667 207,413 969,450 
900,302 207,414 999,797 
207,416 1,000,269 
VI. 308,748 1,010,433 
471,638 1,014,039 
476,413 1,014,633 
613,920 496,435 1,020,670 
649,727 517,473 1,023,199 
649,728 525,627 1,024,081 
1,032,433 CAESS TO 1,028,006 
1,416,621 661.800 1,032,412 
664,450 1,034,898 
Kit: 816,457 1,038,209 
1,004,609 Meee 
263,341 1,149,575 1,042,35 
1,470,555 bear 
I,07 92 
ebets ra 6. 07043 
1,057,430 
43,066 1,054,247 1,088,735 
248,153 1,090,379 
263,420 Developed 1,099,108 
207,414 
688,067 G 1,113,468 
1,232,550 392,723 1,125,050 
1,470,555 673,640 1,128,813 


1,150,675 
1,160,406 

9,344 
1,180,985 
1,183,378 
1,188,545 
1,215,359 
1,237,192 
1,316,781 
1,319,852 
1,323,285 
1,325,841 
1,365,040 
1,371,979 
1,375,701 
1,378,388 
1,416,621 
1,422,866 


VIII. 
261,518 
4 5 


255,349 
XV. 


625,717 
649,218 
675,585 
678,884. 
688,999 


XVIII. 


877,052 
877,053 
877,054 
887,620 
976,417 
978,801 
995,494 
1,026,089 
1,237,192 


Direct 
Til. 


627,896 
648,331 
653,492 
675,574 
675,575 
734,866 


VI. 


3573273 
357,274 
360,792 
366,078 
380,067 
388,185 
396,293 
415,258 
417,204 
417,295 
417,296 
421,640 
423,550 
423,970 
432,989 
440,953 
442,369 


485 


454,645 
462,824 
464,135 
467,162 
476,337 
476,371 
482,106 
483,368 
493,563 
496,392 
498,303 
498,404 
498,405 
408,759 
498,873 
498,874 
499,198 
499,216 
501,118 
501,500 
506,284 
509,929 
511,532 
511,688 
512,493 
516,757 
516,760 
521,095 
521,985 
521,986 
524,069 
524,070 
524,220 
525,492 
532,125 
533,508 
534,573 
536,532 
536,880 
539,699 
544,699 
544,700 
556,298 
5575435 
5571436 
5573438 
558,344 
558,438 
558,613 
560,796 
563,384 
563,385 
563,386 
578,432 
578,580 
5795773 
583,635 
584,981 
588,182 
588,203 
591,616 
601,033 
601,859 
602,855 
602,856 
606,181 
606,264 
606,436 
611,597 
613,640 
613,641 
613,642 
613,646 
614,391 
620,368 
620,369 


620,574 


= DIGEST OF PATENTS 
629,748 1,188 
; eocens 820,379 619,88 
634,000 | 1,210,751 837,775 eipane eee 146 Gi687 893,499 
yee 1,215,359 844,914 620,562 Pants 1,473,887 919,572 
644,238 pga a Mlb er hier 620,563 pe: VIII. 931,598 
648,623 | 1,268,031 sepa bg 894,579 956,348 
652,456 estas Sol cos peers? 899 863 263,341 ere 
656,6 Nae at , 43,502 ; 966,092 
ae acne Beenie? 644,326 Sogee4 | guttide Vat | Ponscre 
658,897 waa. , 40,841 f 1,083,110 
ceaaee kre oats 948,204 647,279 sd ate xy 1,083,489 
1,365,040 970,378 6 915,338 
670,398 I 2 47,281 6 I,105,515 
676,405 pila 985,352 651,453 910,030 523,138 1,128,371 
682,510 1,378,388 992,567 657,539 916,031 Re. 11,659 1,175,230 
ae 1,422,866 993,735 661,871 918,920 560,334 1,247,475 
700,565 VIII. 993,736 662,073 920,156 594,106 1,265,836 
709,186 994,756 662,703 937,040 601,364 1,302,671 
724,893 261,518 998,156 662,754 937,041 609,327 1,329,898 
728,477 XI 998,772 662,755 9375194 611,611 1,449,681 
759,613 ; ant lee 669,794 943,560 614,538 1,465,853 
792,600 254,064 1,008,906 675,217 943,561 620,428 1,471,854 
860,220 255,350 1,008,908 677,239 948,241 629,221 L 
860,221 413,562 1,014,204 680,395 955,410 632,170 akes 
877,643 440,536 1,022,781 690,332 955,699 642,256 Tit. 
877,644 1,032,216 697,545 957,683 649,218 
888,036 XV. 1,038,589 704,804 958,464 657,768 1,090,123 
°897,529 626.2 1,047,812 706,921 958,465 657,769 Vv 
898,217 ae 1,052,507 712,190 959,617 660,770 : 
Teer oe : 1,052,520 712,793 960,671 665,726 378.003 
920,151 59 1,063,000 713,437 961,396 667,486 617,70 
031,423 XVI. 1,076,329 714,000 961,397 673,388 97 03 
931,424 aPaO7 BE 714,042 961,398 675,585 VI. 
933,446 #46,327 Brs07:982 715,074 961,399 678,084 
033,447 XVIII 1,317,160 726,688 063,377 679,199 1,157,525 
Seasaue 1,329,435 727,270 980,140 Re tems VIII 
933,562 32,065 dices by 729,217 984,442 693,632 Ce 
950,404 252,203 1,452,774 Reape 998,596 ee 261,518 
969,450 327; 31,385 2 : 
999,558 471,638 ns 737,836 909:439 695,534 as 
999,797 688,967 233,458 746,965 1,005,481 aes 1,031,823 
Leggs XIX 233,459 Nes 1,012,363 709,151 XI 
> ’ ri ’ . 
pouess : ahabe 7611440 mph 710,766 
1,020,670 é 37698 240, 765,996 anes 723,154 420,164 
I 020,756 17,628 ayo 768 455 1,025,174 727,387 616,622 
1,024,081 Reducin 2 a 772,775 apaeth. 728,623 er 
1,024,308 Vat auoteas 776,884 ae 732,090 898.098 
1,032,412 III 250,036 778,725 me Sryek oe 
1,032,433 : 251,499 778,752 1,042,679 haps 1362 
1,034,898 682,523 251,500 2995077 1,043,468 ern XV. 
1,038,209 692,762 251,501 807,782 Seta 742,189 
1,038,210 724,78 251,071 812,598 f pape te 747,643 772,931 
1,078,926 legis 257,812 823,204 eee 750,113 953,008 
1,079 415 ye 9 257,81 836,309 1,057; 87 7555428 
1,082,923 beget: Peas: 839,099 mite 7631193 XVI. 
j ‘ Ofns 763,320 
vanes | Hits | Bred | gua | reume | geezse liao 
1,088,735 Vacivae 259,261 850,444 Adaya Sd 7751570 pi 
1,090,379 787,859 259,629 856,687 1,133,031 776,264 9097 
1,101 262 856,776 1,144,577 777323 XVIII. 
’ 9739 798,104 1695 977 1,175,63 8 8 
1,125,050 801,418 276,888 860,900 peer. 779,47° 
»41 868 1,188,543 790,167 661,800 
1,150,675 809,892 276,889 : 9755 1,211,413 802,040 1,232,551 
Le eae 809,893 ad ar ge Re Tuas 818,980 1,383,710 
1,169,344 809,894 ei gat he o 1,247,927 820,501 1,478,039 
1,180,935 Sir 105 1,158 1,293,680 : 
471 618,096 88 821,378 
’ 1,442,743 864,644 1,054,247 


ane 


COLOR INDEX 


487 


BROWN 
Acid 1X: Basic geasee 535,036 Reeecoy 658,055 
f 957,999 543,539 658,286 
“a res. ies ge 558,612 III. 660,058 
656,981 XII, 341,091 993,020 558,614 660,067 
656,463 3 462.At4 997,061 563,386 186,032 660,097 
707,374 OFS 879,424 1,009,952 567,413 791,869 661,907 
1,196,422 XVHI Bae ato) | ot aets 588,180 874,743 665,547 
Toyvao4e (| ose! eioes o7 490 674,137 
VI. 980,251 1,021,364 588,182 893,412 681,689 
Boe x6 Basic 1,021,365 588,183 909,800 687,072 
210,233 “ner eicen Sper seh 403 915,385 687,581 
257,242 1,021,365 I 1,025,983 602,858 922,282 688,885 
257,243 | 1,021,366 1,025,984 603,009 925,917 690,271 
260,242 1,023,977 1,455,486 gated yt ied OO 35290 9295443 712,176 
261,175 1,052,135 603,648 935,827 714,542 
261,766 Acid VI. 1,052,262 608,024 935,878 718,342 
261,767 Mordant 1,052,647 611,111 938,565 723,448 
262,620 221,114 1,056,080 613,643 938,566 746,926 
269,359 III. 515,100 1,078,503 613,644 943,717 801,598 
332,820 602,639 1,082,581 622,961 957,040 866,939 
380,928 188,061 ee 1,092,842 644,462 957,041 886,532 
384,316 443,402 1,123,263 647,237 957,042 889,936 
454,645 452,210 420,311 1,126,466 665,696 957,125 895,637 
456,627 511,901 XI 1,173,077 683,190 958,325 897,873 
456,807 643,451 . 1,183,378 693,670 970,278 909,151 
602,858 653,492 - 548,344 1,185,413 718,032 971,225 909,152 
603,648 656,081 2 OE Diede hart 77e 1819 Bae 0a 909,153 
610,349 656,463 985,424 Neha PHz65 06 9931992 909,154 
624,256 686,356 ; 1,327,688 903,284 999,680 909,155 
628,814 707,374 XVIII. 1,338,506 946,050 999,798 909,156 
647,236 793,558 1,365,706 946,051 1,009,981 900,277 
655,529 868,399 1,023,977 1,382,196 946,052 1,018,433 915.385 
658,506 1,090,123 Diteleed 1,405,087 O7T,111 1,028,637 934,302 
658,507 1,196,422 evelope 1,411,245 971,112 1,034,895 034,303 
671,902 II. 1,419,500 978,580 1,044,933 960,652 
671,903 2 XIV 982,250 1,047,813 961,387 
671,904 298,998 ALY. 982,952 1,050,829 961,388 
672,714 424,019 739,071 455,952 oeenee ti? 73553 996,485 
679,053 431,297 ; ; O97;001 1,090,636 999,045 
680,283 452,197 VI. XV. 999,713 1,095,780 1,061,714 
688,647 509,623 1,009,952 1,120,475 1,081,601 
716,289 548,416 515,381 561,276 1,019,321 1,162,496 1,081,602 
719,048 584,460 588,181 900,152 1,023,120 1,209,212 1,096,715 
754,856 602,641 588,182 909,153 1,024,308 1,216,921 1,098,259 
767,069 602,858 588,203 1,025,983 1,261,858 1,098,260 
790,363 655,529 602,858 XVIII. 1,025,984 1,266,896 1,099,039 
823,793 657,064 603,009 1,045,196 VII 1,102,171 
879,053 657,065 603,090 980,251 1,052,135 : 1,112,445 
879,552 718,028 603,648 1,021,304 1,052,647 872,085 1,126,630 
902,186 7371445 608,024 | 1,021,365 oe ah 888,852 1,128,368 
906,421 807,289 610,349 1,021,366 1,074,046 940,586 1,132,922 
053,033 870,552 624,256 1,023,977 1,078,503 943,078 1,165,531 
953,034 936,321 628,814 Direct 1,082,581 968,697 1,187,614 
953,035 981,276 632,503 1,087,428 1,243,170 1,199,697 
964,919 987,362 647,236 III. 1,092,842 1,266,092 1,244,795 
980,251 1,077,492 658,506 1,099,676 1,434,983 1,244,796 
6,466 3 
982,952 1,210,808 658,507 653,492 Ae rs 1,444,277 1,251,368 
987,999 1,216,812 665,696 Tol TOOT 7 1,461,435 1,251,369 
989,001 1,216,813 671,902 VI. 1,183,378 1,268,803 
paate0 1,221,849 eats oye pire XV. 1,308,552 
995,1 I I,2 71,904 2 ’ o I Io I 
1,021,364 peed 672,714 221,116 1,282,355 561,276 Cee 
1,021,365 1,235,253 680,283 221,119 1,283,296 Sulfide 1,318,022 
1,024,308 1,264,604 688,647 302,170 1,310,532 Vat 1,327,862 
1,027,132 1,281,243 693,670 365,409 1,327,688 1,358,490 
1,043,873 1,283,296 718,028 380,493 1,292,385 XV. 1,405,446 
1,052,262 1,292,385 718,032 384,315 1,365,706 ae 1,452,805 
1,076,321 1,338,500 754,856 384,316 501,27 
1,077,492 1,382,196 767,069 384,342 IX. 561,277 Lakes 
1,106,781 1,408,363 778,610 399,581 eager III 
1,199,234 1,411,245 790,363 430,534 599,559 : 
1,199,890 823,793 440,288 1,412,707 603,755 1,090,123 
1,210,808 $0 879,053 454,645 606,193 
1,216,760 870,552 465,116 XIV. 608,355 VI. 
1,216,812 413,724 906,421 491,422 611,610 82.8 
1,216,813 548,236 046,050 503,748 ites 953,005 
1,235,253 946,051 509,623 455,952 41,9 
1,270,325 XVIII. 946,052 509,635 636,065 641,054 At rl 
1,338,506 964,919 514,931 951,046 648,597 Betis 
1,382,196 415,088 Q71,111I 515,381 951,047 650,292 VI. 
1,395,238 998,139 071,112 516,380 951,048 653,278 
1,419,500 1,023,977 980,251 534,539 951,049 653,670 409,384 


488 


DIGEST OF PATENTS 


a EE aE ESE N ne 
eee 


GRAY 
Acid XVIII. XVIII. Developed 493,564 euge 968,697 
495,873 960,182 985,767 
III. dager sbeebs ve 515,339 968,533 985,768 
pearee 1,005,405 673,640 516,203 970,278 985,769 
668,445 ermcetae Basic VI 516,203 971,224 985,770 
723,125 Acid . Boe 975,863 1,005,140 
556 30,079 1,005,141 
863,397 Mordant XIX. eee hea 542,073 : 996,109 16h 6ee 
V. III 423,050 536,879 556,164) vegas i eee 
r 8 672, z : 
6 68.084 stir as die! 571,933 1,044,933 Vat 
73,640 adoas Basic XVIII. 603,646 1,047,940 XV 
mee Mordant 1,099,676 1,052,520 : 
yi: 623,638 4 9951494 1,270,290 1,169,404 
668,445 Direct Reducing 1,464,079 560,334 
515,339 790,079 420,311 Vat 779,860 
672,714 oT VI. VII. 961,387 
958,912 oh 449,629 at 941,152 | 1 ee: 
1,402,350 958,912 454,535 476,393 767,259 954,273 | 1,151,628 
GREEN 
Acid 1,021,364 Acid 1,237,193 661,800 Direct 893,8 
’ ? ’ ’ ’ 93,537 
1,021,365 Mordant 1,242,536 664,450 ora aee 
III. 1,021,366 1,394,823 III. 992,567 
1,199,233 III. eb pee 993,735 
555,904 1,395,823 X. 154705555 631,605 * 993,736 
599,426 xX 348,613 362,835 XIX. 648,331 995,936 
599,427 ; 3991479 548,236 Graibor 1,022,781 
or ’ 
Bee | sveme | derek | fe | comer 
623,219 476,491 . . 1,052,507 
623,220 555,904 eat, Developed ; 1,052,520 
640,986 >a 0 569,405 : 421,040 1,093,427 
548,158 
ee spat | Biol | VE | Gs | sea 
“pleats 1,138,670 SOG 807,181 fo ” 
S42 sores, | Gores | Gort | ee 
’ ? 0 , > ’ 
675,573 XVIII. 617,981 pil Cnt FS af 563,384 1,207,982 
687,657 623,219 XVIII. outils: 585,104 1,216,134 
688,576 412,61 623,220 ‘ 591,616 1,396,483 
707,373 Bae 3 631,605 501,104 980,251 603,645 1,464,598 
715,662 2 the a 648,331 999,028 980,521 603,647 1,478,027 
723,125 ere 654,295 1,460,315 988,000 606,439 
729,073 ; 673,691 993,549 627,679 VII 
734,325 ae aad 675,573 XIX. 1,006,051 628,233 j 
738,614 615,472 688,576 1,021,364 655,013 647,280 
5547 617.6 47; 
778,036 615,485 7075373 el 1,021,365 950,404 699,581 
ei arbee 623,346 Shed ied iia on 1,021,366 974,346 872,227 
12,684 729,073 3 980,521 cea 
826,750 Bees 734,325 si pps, a5) 988,000 360.008 
ate: 8,61 1,024,081 I,00 900,09 
996,487 630,976 738,614 6 2009745 1,001,457 
Pee che eee 778,036 67,486 1,101,739 1,024,080 1,101,7 8 
1,207,981 ead 812,599 Basi 1,150,656 1,024,081 rte 
1,280,648 766,359 812,684 asic 1,150,675 4,802,790 1,444,277 
886,815 996,487 VI 1,193,829 1,126,656 1,466,687 
VI. 891,888 erates ; 1,199,233 the Br) 
891,889 VI 613,920 1,237,192 rahe eee Sulfide 
514,599 980,251 1,416,621 1,241,183 4) Gieae Vat 
562,200 980,521 1,416,621 ee 
563,384 999,028 464,77 ye ages: XV. 
627,783 1,021,364 ge rid eons XI Reduci ; 
646,711 1,021,365 585,104 423,341 Vat” 653,670 
805,918 1,021,366 805,918 1,470,555 86 695,533 
843,077 1,101,770 843,077 eagee III 698,555 
879,053 1,470,554 961,354 Basic 729,874 
906,421 1,478,015 1,155,765 Mordant sigh ons 739,145 731,669 
932,813 1,478,039 1,217,042 6 : 
8 7753397 741,030 
958,830 1,219,954 950,458 8 
961,354 XIX. 1,221,849 AVI: 1,021,364 z Yeak toe BE 
980,251 1,234,994 222,257 1,021,365 Saree apa 
993,549 1,054,247 1,237,192 266,912 1,021,366 876,190 843,156 


s 


COLOR INDEX 


GREEN—(Continued ) 


489 


897,8 1,054,888 
ee ce me | caper 
927,868 1,081,599 1,251,368 1,076,8 gopaet 
. 1,081,600 I 251, 6 ITl. ah te 807,182 1,478,039 
9345303 92515399 
958,640 1,083,489 1,261,394 a 
gee 1,093,259 1,314,929 348,603 XVIII. XIX. 
hapless 1,100,877 1,405,446 615,232 
901,53 1,102,171 1,440,833 1,090,123 1,031,823 661,800 1,054,247 
ORANGE 
Acid 1,233,742 Basic 1,024,0 
5233, 5024,031 5455333 1,342,134 678 
1,270,325 Mordant 1,025,983 611,663 1,362,936 1,082,898 
III. 1,314,921 1,025,984 631,610 1,365,706 1,243,170 
9.35,506 iG 1,032,797 631,611 Meee? 
6 1,407,711 £052,135 644,462 Mil: 
ee 70° eee 1,074,429 662,122 XII. 
x 510,577 1,078,503 663,498 
VI. ey 1,078,504 675,629 656,858 852,158 
43,509 1,094,448 675,632 : 
211,671 740,4 1,126,489 677,517 
22%,120 ALI. 746,981 1,128,813 678,423 601,063 XIII. 
225,908 766,540 1,147,803 763,761 636.065 8 
251,162 1,026,257 794,052 T,US3,355 889,016 weg eeak 52,158 
207,852 1,005,176 1,133,370 902,186 sae 
310,155 Acid 1,255,740 1,185,413 903,284 951,048 XV. 
329,634 Mordant 1,418,852 I,210,808 916,161 ; 
333,042 1,215,359 935,018 , 746,926 
531,975 XIX. 1,270,325 936,367 Reducing 760,110 
601,063 III. 1,314,921 959,109 Vat 895,637 
659,497 625,536 1,338,397 982,507 896,916 
716,289 702,445 1,338,506 993,073 III. 899,456 
719,048 Developed 1,342,134 995,160 ie 
719,049 1,362,036 999,944 1,115,1 
724,078 vi. VER 1,365,706 1,001,183 sees. 1,251,368 
767,070 1,405,687 1,006,929 993,992 
787,767 221,117 241,661 1,453,660 1,015,375 999,798 Lake 
798,098 225,120 631,610 1,457,114 1,024,031 : 022,781 VI 
879,552 297,852 678,323 1,025,983 1,023,248 c 
902,186 Ase 679,172 XIII. 1,025,984 1,025,195 8 6 
943,536 Eee NS ee 1,032,797 | 1,034,895 ee te 
949,633 Soar iret 852,158 | 17951859 | 1,044,603 a 
‘ aye 718,028 765,080 i 1,052,031 1,052,480 860,575 
he 7 870,552 865,587 Direct 1,052,135 1,087,243 912,138 
989,954 936,367 879,552 aie? 1,067,881 aeaor: 914,146 
991,750 943,536 889,016 1,074,429 1,067,046 935,371 
993,549 1,014,114 914,144 VI. 1,078,503 a akg ae 959,078 
1,005,233 1,210,808 916,161 1,078,504 eer 1,022,612 
1,014,114 1,216,812 949,633 375,930 1,094,448 foanees 1,028,493 
1,126,489 1,216,813 982,507 395,634 1,147,803 1,419,302 1,034,853 
f 128.813 ae 991,750 401,483 1,153,555 115156 1,314,921 
993,073 430,534 1,172,061 : 
1,172,061 1,292,385 8 Oil and alc 
eee Bean cn6 993,549 447,303 1,183,37 VII a 
x4 1330,50 999,944 497,032 1,185,413 : Sol. 
1,216,760 1,314,921 1,001,183 500,761 1,215,359 VI. 
1,216,812 1,338,397 1,014,114 519,523 1,292,385 872,585 
1,216,813 1,338,506 1,015,375 524,261 1,338,397 915,346 1,314,921 


490 DIGEST OF PATENTS 
RED 
Acid 313,118 84 
35137 XIV. P 
ae 314,938 843,149 si bar od at Basic 
; 314,939 843,756 386,709 779,82 1,302,19 Mordant 
6 8 329,634 846,511 Ra66 : xX 
Ape 332,528 863,290 XVII 826, a ve a 
oe 332,830 865,252 Me Bote 
saarge 333,038 865,253 8 + 3 440,359 666,095 
ore 333,041 879,552 250,201 Spteey | 709,187 
656.463 333,042 880,292 250,247 eee XVII. bir as 
659,565 333,257 887,348 262,680 a pete | 716,264 
65955 334,257 902,186 318,484 < 9123 262,680 766,540 
8,576 344,971 906,421 333,049 siege 603,300 794,052 
707,374 357,274 043,536 421,049 1,446,163 609,598 1,418,852 
763,233 376,392 949,633 473,453 877,052 1,455,486 
779,825 380,928 961,355 603,300 VI. 877,054 
B06.054 441,045 982,952 701,427 947,876 Vv. 
glad 447,189 982,053 877,052 213,563 976,417 
Eoeapee 454,645 982,954 877,054 213,564 978,799 543,894 
ee 456,627 982,955 887,620 221,118 hese oo hhpeercd 
75,390 456,807 986,287 947,876 256,380 999,028 559,062 
932,290 458,283 980,054 950,359 207,852 1,023,977 559,063 
958,850 458,284 993,549 076,417 314,9 592,608 
994,803 466,841 1,008,907 978,799 senee XIX. 
995,306 468,142 1,012,055 978,800 441,045 VI. 
1,026,557 493,583 I,O014,114 980,251 458,28 573,299 
1,026,621 500,762 1,023,199 999,028 prey 1,002,825 221,118 
1,037,410 512,116 1,024,308 1,006,738 ORaee 1,055,864 602,637 
1,062,990 515,764 1,042,198 1,023,977 512,116 1,055,885 626,935 
1,086,123 525,057 1,054,348 4,020,059 631,685 1,403,888 
531,07 1,075,30 1,219,166 VII. 
Vv. 558,613 eae is Basic 
: 561,615 1,113,622 XIX. 704,826 913,513 
425,530 563,383 1,123,430 718,028 t 
430,975 610,345 1,126,489 739,069 XI. 
431,404 617,963 1,128,813 ees 787,046 516,588 
Ee eke Wel ee Cae: Rowe oats hae 377,349 
’ 59,49 1,154,826 : 7 . 377,350 
| Sees | ere | Sil | Rs 
690,204 1,199,890 pyegak B06 ae Sa XIII. 
204,799 695,238 1,201,544 eaett I 826 281 240,136 
Re. 9,144 695,811 1,201,808 646,794 826. 28> 466,826 257,917 
210,054 700,565 1,216,760 esog ih 827,468 567,473 
pe ato283 704,825 1,216,813 apie 841,371 $98;508 XVIII. 
e. 9,986 704,826 1,233,742 yr rie as Spans tA 7 eons 
Re. 9,987 713,507 1,286,411 i He hs 50,335 
211,180 716,289 1,314,921 Acid 843.1 ws 53,241 
eae by hip) 1,316,781 Mordant 843,756 Sons 248,154 
»071 722,71 ees ets : 02,037 
213,563 724,078 a ari II. eevee St 6,352 283,766 
213,564 727,962 1,358,007 865,253 879.424 310,128 
224,927 727,065 1,359,069 : 6 879,552 Labeisigee 316,471 
224,928 727,966 1,382,196 34:07 887,348 1,074,046 471,638 
225,908 737,967 15393.712 924,232 1,087,427 580,766 
233,465 739,069 1,395,238 Ill. 933,841 TAS 2 aS0% 602,637 
242,707 741,930 1,408,405 936,367 609,598 
246,221 754,315 1,419,500 95,465 043,536 aN 661,800 
246,272 761,123 1,429,782 97,597 049,633 664,450 
249,926 778,476 1,467,711 127,426 961,355 780,741 913,513 
250,038 787,767 153,536 964,768 913,514 
251,163 787,768 VII. 154,153 983,132 XX, 947,918 
soe 790,364 188,061 986,287 949,906 
ee 792,032 677,239 188,217 1,012,055 402,436 1,023,977 
eid 792,034 891,690 446,893 1,014,114 425,504 
gd 797,441 500,917 1,114,771 445,684 XIX. 
56,37 7975731 X. 569,404 1,127,261 489,623 
256,380 7975732 560,418 1,210,808 16,588 
256,401 803,592 00.8 aide 510,5 425,504 
300,874 646,795 1,216,81 516,58 
oeR tre NAT pgs Re 3 »589 425,684 
ee me Pais 650,756 ree oe aa ae ieee 
’ 20,2 ? ’ 
268,507 826-281 gore shied + ph 578,578 516,585 
, 440,359 656,463 1,286,411 584,119 16,588 
277,182 826,282 466,852 675,574 1,314,921 &. Sieg 
eRthae 827468 1314, 596,333 516,589. 
688,576 1,316,781 613,926 8 
meta ee tae XII. 797,373 1,323,285 625,641 78,578 
‘ 1,371 ‘ : 
302,970 842,548 808,919 At et ee es ap oe eke 
’ > ’ 
3035335 843,077 1,026,257 763,233 1,338,414 821,452 fie Bl 


. 
. 
é 
i 
z 
7 


COLOR INDEX 
491 
RED— 
bas (Continued ) 
536 
625,6 999,2 
yey ree 980,251 
643,37 1,014,11 1,023,977 588,180 
fag. ; 1.018, 4 1,026,08 588,18 1,024,308 
45,781 2015,375 ,009 y1OI ’ 
656,426 1,020,670 1,219,166 588,182 1,024,794 791,869 86 
694,149 1,022,287 588,203 seabsse2 875,390 Slane 
605,441 1,022,288 Direct 593,347 pn Oaae eal die 
716,264 1,023,199 apeeihe Pe de Ed 939412 net ioe 
738,227 1,026,902 IIT, pa cee gigas ake ee gee 
821 1,032,7 22,961 041,146 928,891 2949 
9452 I 97 62 I,051,8 92 876,3 
D 3033,310 675,574 6 5,174 ae 3059 Pane 877, 39 
eveloped 1,042,356 1,327,260 bie bio heat 459 entees 
I Reras® eae? Poets Li 887'6oo 
. 9052,137 VI ,O2T = 9137 97 OL 8 ’ 
ae 1,058,562 : alte 1,058,502 935,827 eee 
076 1,058,692 3,498 ,058,692 35,878 897 
: Jeb larttes 221,118 666,867 1,065,950 038,565 eee 
646 1,074,429 56,375 675,629 1,071,833 950,344 5738 
uae 1,075,305 Oe Sk: 675,632 1,074,429 955,105 99,152 
VI. 1,078,504 tc ,380 677,516 1,074,946 957,039 910,839 
1,082,925 a779102 677,517 1,076,756 957,040 915,346 
211,525 1,087 59335 678,323 1,078,504 957,041 916,029 
241,661 1,0 pare 329,632 679,9 1,082,92 957,0 916,030 
404,097 Rooted 329,033 087.171 13082,925 057,125 923,959 
578,580 1,09 342,432 700,565 1,087,430 961,047 949,592 
588,181 Renee 344,971 718,032 1,092,842 961,612 963,813 
588,182 1,122, 3575274 718,389 1,094,448 970,278 965,170 
588,203 speree?: 359,576 724,894 1,098,388 986,521 para bt 
git | fact | Heat ee | baeee | Be pe 
39,042 1,128,8 1806 79,177 1126,656 93,735 mares 
6 ,O13 362 I 1,074, 
eroca | 1188825 2 ae hg Uressss sag 1308,778 
Se hs ie lee 365,666 pea es Tere spre porate Pre a 
fos.812 rere ser 365,667 806,0 et aes 1,004,4 1,147,778 
695/812 | 1'160,408 375,848 807,110 185,41 net ot tet Seseyet 
718,028 eee bipan 380,067 ee Paib ex 1,009,081 Ageia 
718,032 i eBe at beaten 813,155 I,215,359 1,010,463 461,435 
722,715 1,188 $46 Sp ee 837,736 1,232,056 nat cs Sulfid 
722,716 Tiger 301,132 839,360 1,282,354 1,011,068 ide Vat 
724,078 aes hos seat: oleae 1,283,206 T,014,204 XV 
727,962 1,215,359 : 9,127 Siem 1,292,385 epee : 
727,965 1,232,056 94,425 873,798 93395397 Does 523 
macs | tales | Bi eet ee are saat 
See gee 401,483 886,095 iesese 1026 5688 723,448 
oie 1,316,781 404,331 888'so0 1363-886 1,028,6 818,980 
770,1 z 1,323,285 406,669 888,8 1,365, 6 ama ey 829,740 
778.476 — 410,057 889,016 114721333 ga lia oetene 
’ ’ 
Mee | ate | Geek | Belt rapeaie | aseese | Hestzi 
790,364 1,342,134 ce, 4 3,284 x pied ged 1,098,2 5 
7975441 1,362 2149 912,182 VIII. ’ 3 »589 I,1I u 59 
806,41 1936 416,145 916,16 1,047,831 115,188 
807422 Gecgah 47,207 916323 318,48 71050;820 1,128,368 
813,155 des ad eh 931,423 aN beet 28 1,129,875 
‘ ’ 423,56 931 : 1,065, 3129,575 
a edhe 1,419,500 eh ds Le OLE: puttaee seer PE 1,261,304 
Slegs340 aay 429,350 9330447 ssa 1070,106 1,452,005 
’ 4 ’ ’ 
gest wssio6o | aazrdo |  agise2 |X 497 | Prosioos 147 4150 
3,290 XIV. 2045 3562 xX ’ 3004 La 
ae sib) | bano8k vases | an 
887,348 4551952 483,308 943,470 3775349 1,133,081 ae 
889,016 XV 498,303 978,580 ae ony 1,162,496 1,090 
ante | Bere | pases foes | bas726 Ag 
F, ’ ’ 2 m 
916,161 829,740 516,756 982,952 pi se 1,285,727 
916 16,75 989 ’ 9329 
ed XVIII. $10,522 ear ee eat aae ds 
941,088 19,523 999,230 Hthg VII. VI 
949,633 tes See ede ie pe : ? ‘ 
’ I 00, ’ 
ge 88, aoe 532, 6 91740 645,781 ral 650,747 
ees ed 20 eeu »012,055 aa 690,294 
982,085 9761417 $35,037 | or.a75 Reming 10.348 | Gg9181: 
993,549 978,799 555359 5020.6 3 841,003 yee 
978,800 572,723 ae 848 Te 
578 1,022,28 IIl. 1354 718,356 
1,022,288 9355 724,743 
186,032 850,827 724,894 
867,305 728,388 
728,455 


492 
DIGES 
T OF PATENTS 
RED— 
(Continued) 
733,280 g 
30,312 
741,029 8 ? 9 
37,128 32,289 
743,0 978,86 
tgs 858,065 aca paatves eee XI Oil and 
757,109 eae ees 983,486 scr ; Alc. Sol. 
’ ? F 
730,716 Sorte, 942,916 1,001,286 1,073,784 1,065,063 VI. 
765,079 872,181 954,960 1,001,458 1,073,902 402,980 
770430 878,96 955,068 1,032,055 ee waht th peda 
786,767 888 81 964,786 1,014,539 gab ei XVIII. 
789,096 oeoet “ 1,022,61 _ 1,073,951 661.8 
792, : 908,580 964,918 I O28. 1,097,231 agate 307,401 
ohehes 911,186 964,920 Phases 1,145,072 oe 589,766 
ye peeaar oe ee XIX ggesior 
»401 1038.884 1,314,921 : XIX. 
1,358,007 613 11 
113 1,381,503 
VIOLET 
Acid 
Pees 547,17 
III. 41,936 9173 6 
754,856 Neg yas peers 531,148 
617,08 765,581 238,870 655 x5, 547 329,636 
648.3 I 767,070 66,594 Bien 353,264 Goad 
656,081 778,476 XVIII. ast 856.537 77279 | 947,918 
656,463 792,032 7 ’ 3 863, 949,906 91 
’ 49, 3907 1,02 
666,594 ‘heeded leet eet 893,855 XIX vous 
pase 523,703 346,022 763,233 Bat 1,402,195 
432 ; : 77 2,8 »040 
7291073 pices Ce. Tote | eee 41p048 | 
2 3 ’ ’ 1,0 : 613 ’ 
set ety sees ees | ree || can 
35233 Raa 498, : 
gees | 8437 sie | vt | Dereiaeae 
_os8,830 | Baa.zse Sonast | 42072 | 304708 Basic I. 
Foneats 843,808 611,628 420,374 Se Mordant 
1,139,540 ene ase pe pis WI 134,076 
Vv. 899,171 877,052 634,005 ya Be VI. 
901,676 947,876 piece 877,052 503,295 
940,354 912,356 950,359 eae 877,05 583,439 
Vv 921,105 976,417 792,032 047,8 3 IV. 588,181 
I. Re. 13,121 978,799 pete e aioe 603,008 
921,239 978,802 35,539 EEE pope 677,279 608,999 
356,672 Re. 13,122 980,251 839,489 I,o1 1799 689,025 610,349 
381,045 935,031 986,287 841,371 ape bs 5 613,646 
yi046 961,354 995,494 843,077 15034,173 V. 650,619 
454,645 982,954 1,023,977 843,137 1,042, fe 664,955 
456,627 ances 1,042,498 843,149 erpese 369,764 676,495 
456,807 986,287 1,065,405 431756 1,065, ‘ 418,916 677,227 
408,142 roaea6e Re. 13,069 865,253 Re. ieee 458,281 677,228 
476,335 | 17014,039 1,217,238 887,348 ee 677,229 
525,056 1,024,308 1,218,232 933,841 11375,701 VI. 677,230 
546,068 1,028,006 1,219,166 935,031 iets 677,231 
583,439 1,052,262 1,387,596 961,354 bt ot 221,116 692,675 
5935347 1,054,348 986,287 sei 4 602,640 692,676 
602,640 1,078,925 XIX pron doe XIX ' 710,05 
paras 1,106,781 é : rie ‘ XI. 7i8vaa8 
065 I,126,48 09, ’ 771 *< 2 
655,520 sbiarteaa: 9,997 1,127,261 1,003,257 396,87 a 
664,955 1,216,760 Acid 1,234,994 Basi mee 727,963 
671,896 1,237,183 Mordant 1,242,536 : 985, : 727,965 
677,227 1,325,841 1,292,385 V on 727,967 
ee 1,359,969 Il. eee . XVIII 729,601 
77,229 | 19375970 338,414 248 741,936 
677,230 1,382,196 134,076 1,426,189 oe 754,836 
677,231 1,395,238 Il E eaete Ped see = 
10,059 1,402, . uh: ’ 2 ’ 6 
725,848 /4t9, 800 446,892 VI mie: bee 
726,695 1,429,782 446,80 252,273 i pr 778,476 
727,963 496,1 S 252,273 6 or os 807,422 
727,965 XI »T39 253 02,640 97,415 8 z 
ee ; ae ere 879,424 arate Sseees 
728,021 4% 440, 308,748 839, : 
920,601 440,359 509,439 ceraie XVIII. 325,827 ie 
531,148 6 7,951 518, 3 325,828 8 3,077 
43,451 045 329,636 43,137 
524 ) 43,066 8 
1235 290,892 pane 887,348 
471 ’ 
1638 912,356 


COLOR INDEX 493 
VIOLET— (Continued ) 
916,323 XI. 468,049 1,009,796 707,813 VII. 779,860 
920,151 483,368 1,009,797 931,598 760,167 
935,031 1,138,670 493,563 1,012,960 ‘ 836,309 796,443 
982,954 516,758 1,020,670 Reducing 848,356 818,980 
982,955 XV. 516,760 1,020,756 Vat 872,115 821,378 
999,797 521,096 1,024,308 876,158 829,740 
1,003,26 778,713 534,573 1,038,209 III. 877,743 915,385 
1,009,796 829,740 543,212 1,038,210 he 931,598 
1,009,797 §57,43 1,049,109 647,280 894,00 960,919 
1,014,039 XVIII. 563,386 1,052,136 781,085 898,452. 1,129,574 
1,020,670 576,511 1,058,562 809,892 899,994 1,471,150 
1,028,006 877,052 588,180 1,079,415 818,336 904,867 
1,038,209 877,053 588,181 1,113,468 818,992 916,030 Lakes 
Re. 13,550 950,359 593,347 1,160,406 837,775 041,152 
1,038,210 976,417 602,540 1,169,329 867,679 947,030 III. 
1,052,136 978,799 603,008 1,209,154 906,367 955,699 
1,052,262 978,802 608,999 1,210,751 935,827 997,260 10908124 
1,056,080 980,251 611,507 1,282,354 938,565 1,001,919 Bae 
1,058,562 995,494 613,646 1,282,355 938,566 1,050,179 V 
1,078,925 1,023,977 656,619 1,282,356 950,343 1,051,856 : 
1,079,415 1,219,166 671,896 1,292,385 950,344 1,108,056 
1,113,468 676,495 1,338,414 957,041 1,108,057 418,916 
1,126,489 Direct 687,171 1,342,134 957,042 1,144,577 
60,406 692,675 1,472,333 961,047 1,147,778 VI. 
1,160,40 boo kre 
1,169,329 VI. Oa97 1,472,334 961,048 1,243,170 
Say 724,893 970,278 1,444,277 420,372 
1,209,154 724,894 VIII. 724,894 
1,213,07 344,971 6 9935735 Iphid 8 
1213,075 360,792 759,613 261,518 993,730 Sulphide 20,052 
1,325,841 365,409 7705177 1,003,268 Vat 964,920 
1,338,414 380,067 807,422 XIV. 1,014,204 1,003,266 
1,342,134 380,098 860,221 1,016,604 XV. 1,016,307 
1,375,701 401,483 Hla 350,230 1,032,216 1,073,905 
1,382,196 406,669 775044 XV. 1,038,589 608,354 1,073,951 
1,419,500 423,569 897,529 1,044,603 651,122 1,097,231 
hes 440,639 898,217 608,354 1,047,812 656,631 
447,302 er 656,631 1,047,813 665,726 mele 
454,645 920,151 1,058,604 701,435 
Vit. 456,628 9335447 pe Soe 1,062,075 7775323 396,574 
462,824 999,797 32,965 1,128,836 778,478 410,733 
261,518 464,566 1,009,741 471,638 1,200,848 G7os753 420,164 
YELLOW 
Acid 798,098 1,216,813 Xd 980,251 431,297 XVIII. 
839,605 1,270,325 999,028 452,197 
III. 840,690 1,286,411 6 1,430,899 484,521 415,088 
849,739 1,314,921 bale 528,965 603,300 
621,679 879,053 1,338,506 ermeee Acid 555,058 999,028 
656,463 880,203 1,447,485 59593 Mordant 626,913 XIX 
1,062,990 901,675 935,370 695,238 : 
1,076,249 902,186 VII. 935,829 III. 718,020 6 6 
935,830 pte 
906,422 ee 739,069 702,445 
VI. 961,355 540,564 His des 348,613 818,981 1,055,864 
965,882 994,988 972,951 443,402 936,367 
“eben 978,438 982,050 452,210 961,354 
210,233 978,439 IX. 1,010,919 618,000 961,355 Basic 
211,525 980,251 1,098,600 619,574 1,075,134 
211,671 980,521 225,108 1,109,919 621.679 1,114,750 A b. 
329,908 984,900 2445757 623,069 1,127,234 
253,598 987,999 256,379 XIII. BREE 1,127,261 1,418,852 
289,613 ; 283,265 z 
991,750 656,463 1,149,231 
297,852 289,543 1,210,808 VI. 
1,003,293 8 290,585 702,445 ’ ’ 
333,035 1,028,139 sours 890,588 1,026,621 1,216,812 
333,039 1,041,919 324,615 90, 1,216,813 aye 
380,928 roe 333,036 1,197,632 SG 341,99 
1,054,348 ge IV. 1,204,004 344,075 
pet 1,075,305 . eee XIV 1,283,296 602,638 
71544 1,084,363 743577 . 720 920 1,286,411 879,424 
695,238 nea 6 1,059,571 , 
113,022 1,314,921 902,021 
719,048 6 1,162,109 
719,049 1,157,109 1,299,171 395,115 VI. 1,338,506 1,087,427 
739,065 #n186,346 1,349,802 1,474,587 
739,069 1,172,061 1,380,186 XVIII. 253,598 XIII. 
791,524 1,199,890 1,393,714 297,852 IX. 
791,525 1,210,808 1,396,001 308,912 309,882 256,599 
791,526 1,216,812 1,413,914 603,300 424,019 1,162,109 290,585 


494 
DIGEST OF PATENTS 
YELL ogee 
OW—( Continued) 
XVII. VI 
: 1,157,169 
468,549 
412,979 221,115 epetaeh! 588,180 cavans 1,065,440 III. 
ees 515,100 Dare : 619,518 406 1,070,196 
446,009 602,638 rat 1325 622,961 shel 1,087,293 4a 
XV 626,913 2314,921 656,120 4 brie 1,089,221 1013 
III. 1,338,506 663,498 per ees: 1,090,621 VI 
oa XIII. sean 806,077 ao 1,096,731 . 
90 1,405,687 902,186 1,120,475 
1,232,551 290,585 935,016 Pes 1,196,127 714,883 
x XIII. 935,017 i166 1,209,163 844,845 
IX. XVII. ah 935,018 6G Ce 935,371 
115 936,36 1419,302 971,76 
piricas 412,078 et necuee 1,431,656 eg 
33,883 xV XV. 971,762 . riges 1,001,286 
475,0 
Basic III. uer ase spony III. 478,061 1,051,565 
Mordant 283,766 738,027 999,230 730,1 XIII. 1,059,599 
1 395,080 XVII 999,944 £08 765 ewe 
. 664,450 I. 1,001,183 Ss6sg0 852,158 We cc 
1,012,853 a9: 9050,155 
8 ’ 8 37,8 (8) 
wea | ne, |” ee | te | ea noon 
526,577 Cree XXII. aagaae ee VII ae 
546,177 eee 406,952 ee 922,282 : 1.266608 
617,340 ; . 1,078,503 chap oF 1,074,850 1,314,921 
619,577 Developed Direct 5.098 bo4 935,827 
637,183 rekdone 935,878 XIII. IX. 
643,569 II. I. 1,082,925 eb: 852,158 
1324 1,087, ’ 763,756 
666,0 382,8 pea gh 938,618 x 
666,006 7395145 832 1,094,448 938,619 Me 932,266 
675,568 VI VI. 911 4,044 941,320 561,276 955,080 
yooares d 1,125,073 957,040 561,277 1,051,565 
712,421 211,525 221,115 1,125,074 957,041 OT2.7 47, 1,059,599 
716,084 aat.o6t 221,117 1,147,803 957,042 718,342 1,076,819 
716,264 718,028 329,638 1,153,555 ae 722,630 1,086,155 
7395771 765,080 329,639 1,159,386 i: ee 738,027 1,091,148 
739,117 879,053 360,792 1,160,471 es, sie 7731346 1,166,808 
740,468 980,251 380,067 1,172,061 paonee 782,905 
746,981 980,521 380,098 1,210,751 onrak 785,675 | XII. 
1,005,176 987,999 380,403 1,283,296 1,004,433 he 5 
1,255,739 991,750 380,928 1,362,936 1,009,981 So a4en 9351370 
1,255,740 ie 386,192 1,015,329 892/456 988,870 
1,418,852 eons 396,204 XI. 1,076,036 896,016 
1,427,431 ai asies 398,990 ue P NOLeeay 899,845 XIII. 
1,455,486 1 24.0 : 401,024 se 9057 yee ree 904,809: 
1,455,487 poeee. 401,634 56,859 ae 96 996,485 852,158 
1,455,488 $ 9135 406,670 658,593 np »003 1,061,714 
059,670 428,629 9042,931 1,100,877 XVIII. 
IV. 1,075,305 430,533 XIV. 1,044,602 1,115,188 
1,078,503 430,535 ey OE 1,115,189 763,756 
201,802 1,078,504 454,840 350,229 one 1,140,745 1,232,551 
488,430 1,082,925 472,121 360,553 mB TS 1,440,833 ; 
720,920 1,094,448 500,761 395,1I5 1,052,480 vI 
1,114,844 515,807 396,527 1,055,287 Lakes 3 
V. 1,123,263 516,468 613,911 1,059,607 Oil and 
1,147,803 ep tea 636,065 1,062,975 I. alc. sol. 
543,784 1,153,555 519,523 951,046 I 062, 88 
524,262 951,047 bro 1,427,431 
’ 1,065,102 1,427,432 409,384 
’ 243 1,314,921 


COLOR INDEX 495 
VARI-COLORED 
Acid 1,314,926 1,259,499 X. 357,274 1,457;235 630,952 
1,414,614 1,292,385 te eed 1,314,928 
Y 420,311 390,79 irec 
ve Ix. 1,314,921 380,067 ea 
P 1,314,926 XVIII. 380,098 VI 1,346,154 
1,340,69 1,059,571 1,414,614 380,402 . 
fl 1059, oes 350 segtoe 636,065 Lakes 
‘ : 1,355,04 380,927 : 
XII. XVIII eee 401,483 ied VL 
Beles: 808,919 609,599 stad 438,657 951,048 
221,119 1,026,257 999,028 VI. 421,640 1,314,921 
225,908 423,569 XIV. 
420,634 XIV. Basic 211,525 430,534 XVIII. 
333,042 241,661 454,645 636,065 
947,661 386,709 V. 517,533 462,824 951,046 1,232,551 
357,274 588,182 oe 951,046 ee 
pours 980,251 VL 588:203 eae Reducing dtc teal 
454,645 999,028 710,059 sbdkicid Vat , 
456,627 ; 718,028 543,212 
’ 341,991 6 6 VI. 
456,897 Acid ali i 563,38 III 
541,859 M rd t Biases 980,251 588,180 ‘ 
710,059 Aas Becton 1,052,135 588,181 ids 1,314,921 
716,289 VI EsSt Ass * a ple 588,182 5s a aa 1,314,922 
8 " 1,314,922 ate sh 04, 588,203 ayes 1,314,925 
795552 1,183,378 1,059,607 
02,186 
887,348 297,852 1,314,925 1,210,808 hia 1,123,390 
902,186 380,927 1,215,359 903,284 1,437,783 Photo Sen- 
- 906,421 424,019 XVIII. 1,314,921 933,447 sitizers 
832,813 493,413 ; 1,414,614 eee pes VIL. 
980,251 18,028 1,232,551 1,052,13 XIII. 
1,024,308 if 1,232,552 XVII. 1,067,881 1,243,170 
1,052,262 oleae 1,183,378 752,323 
1,054,348 sit haa Basic P0254 1,210,751 Suifide 805,143 
bak 465 933,841 Mordant 1,215,359 Vat ; 
1,216,7 Direct 1,338,346 
1,216,813 1,210,808 1,282,355 3 
1,259,499 1,216,813 Vie vr 1,292,385 XV. 41331349 
1,314,921 1,221,849 1,314,922 1,374,871 
1,314,922 1,233,433 626,935 344,971 1,314,925 549,036 1,374,872 


INTERMEDIATE INDEX. 


Intermediates listed in this index are those given in the patent abstracts as 
materials used for manufacture of dyes or other finished products, except Group 
XXII, in which methods of manufacture for intermediates themselves are given. 

The chief function of each intermediate in index and abstracts is shown in 
bold-faced type. Ring compounds are used as chief functions except derivatives in 
which a primary function exists in the side chain, such as phenyl glycocol, in the 
indigo group. Numerals multiplying the chief function are included as part of the 
index name. Diphenylamin and triphenylmethane, for instance, may be found 
under “D” and “T” respectively. 


The order of index compounds is from simple to more complex, regardless of 
figures for position numbering. That is, 2-amino phenol is followed by 3-amino 
phenol and by 4-amino phenol, before more complex compounds; 2-naphthol follows 
1-naphthol and both precede derivatives of either. There is but one exception in 
the alphabetical order of chief functions. Amino naphthols and derivatives are not 
indexed with naphthols, since the method of numbering commonly employed is 
based on the position of the NH, and not on the OH substituent. That is, 2-amino 
8-naphthol to be correctly classed as a naphthol, should read 7-amino 1-naphthol; 
I-amino 6-naphthol should be 5-amino 2-naphthol. 

Esters and ethers follow immediately after the acid or phenol. Letters in 
parentheses refer to subdivisions of abstracts in Group XXIV. For general pro- 
cesses see Alkylation, Carboxylation, Diazotization, Halogenation, Hydroxylation, 


Nitration, Oxidation, Purification, Reduction and Sulfonation. 


Abietie acid: 
VI. 1,414,614. 
Aceanthrene quinone: 
III. 1,216,134. 


Acenaphthene: 
XV. 1,358,490. 
XXII. 1,439,500. 
4-Oxy 
VII. 998.596. 
quinone 
VII. eit 904,867; 91513405 a 
905,170; 1,001,919; 1,061,596. 
XXII. 1,439,500. ; 
Acenaphthenone: (See Acenaphthene 
quinone). 
Acetaldehyde: 
XXII. poe 11306,9633 1,421,743; 
429,050; 4373403 
MRIV. Uh vekooes) 
Acetal, Amino: 
XXIV. (m) 1,432,291. 
accceraan 
TX. 759,657. 
Chlor 
XV. 688,999. 


eaeny ethyl oxy 
XXIV. (m) 1,375,949. 
Acetamidin: 
Diphenyl amino thio 
647,281. 
Iso nitroso diphenyl 
647,279. 
Acetanilid: 


XV. 636,066; 687,072. 


XXII. 574,395; 574,396; 578,384. 
XXIV. (m) 543,214; 615,828; 615,820. 
Aceto 


VI. 617,544; 990,173; 1,028,139; 
1,082,719; 1,086,155; 1,125,074; 
T,150,350s55 1,210,512> 


XXIV. (m) 503,748. 
Aceto, 4-carbo 
VI. 1,125,073; 1,526,413. 
3-Amino 
VI. 1,023;120: 
4-Amino 
VI. 462,414; 599,532; 697,765; 
969,450; 1,014,633; 1,014,984; 
1,020,670; 1,074,429; 1,087,429; 
1,090,379; I ,283,2313 1,378,388. 
4-Amino, 3-sulfo 
1,024,080. 
2-Chlor aceto- 
VI. 1,051,565; 1,059,599. 


3-Oxy 
XIX. 694,149. 
Acetic acid: 

XXII. 505,787; 596,043; 667,358; 
715,748; 1,306,963; 1,430,304; 
1,449,918. 

XXIV. (m) 801,158. 

anhydride 

TIL, 8§3;04 5s 
VII. 618,096; 690,332; 690,346; 
778,725. 

XXII. 683,464; 1,298,356; 1,306,963; 
1,311,158; 1,338,979; 1,368,789; 
1,403,920; 1,425,500; 1,429,650; 
1,430,304. 

XXIV. (m) 710,005. 

ethyl ester 

XXII. 1,425,625; 1,425,626. 


phenyl ester, (See Phenyl acetic acid). 
vinyl ester 
XXII. 1,449,918. 
Aceto-, ethyl ester 
VI. 818,981; 1,051,565; 1,166,346; 
1,270,325. 


XII. 658,593; 982,050; 988,870, 
1,098,600. 
XXII. “4,425,626: 
XXIV. (¢f) 743,305; (m) 307,399; 


1,419,092; 1,429,922. 


INTERMEDIATE INDEX 


Aceto-, iso propylidene ethyl ester, 

XXIV. (£) 743,305. 

Chlor 

VI. 658,506; 671,902; 671,903; 

671,904. 

VII. 540,564; 617,651; 619,884; 
620,442; 621,652; 622,139; 
699,581; 712,190; 818,341; 
823,294; 841,456; 850,827; 
867,305; 867,679; 868,294; 
872,085; 877,702; 877,743; 
881,158; 881,159; 881,624; 
888,852; 892,897; 906,029; 


1,001,457; 1,243,170; 1,419,720; 


1,442,743. 
Mel, 15359,071. 
XXIV. (m) 624,772. 
Chlor, ethyl ester 
POPE 2 1,303,101. 
XXIV. (m) 1,086,881. 
Dichlor 


VII. 310,604. 


a-Diethyl amino ethyl aceto-, ethyl ester 


XXIV. (m) 1,429,992. 
Oxal-, ester — 
XII. 627,690; 935,370. 
Oxal-, phenyl ester 
XXIV. (m) 543,579. 
Acetindoxyl: 
VII. 899,994; 960,008. 
2-Acetoluidin: 
VII. 867,679. 
4-Acetoluidin 3-Nitro: 
VII. 867,306. 
Acetone: 
VI. 700,565. 
VII. 257,814; 257,815; 276,890; 
540,427; 662,073; 677,239; 
726,688; 1,412,038. 


XXII. 608,019; 648,389; 690,724; 
1,411,529. 


XXIV. (pl) 1,397,144. 


Acetophenone: 

arsonic acid 

XXIV. (m) 1,425,929; 1,425,930. 

2-Thio 

XV. 893,499. 

Acetothienone: 

XXIV. (m) 1,350,408. 
Acetyl, Brom diethyl, isocyanate: 

MXIV. (m) 1,424,236. 


Acetyl chloride: 


VII. 647,263. 
XXII. 910,648; 1,359,071. 


XXIV. (m) 1,350,408; 1,399,144; 
(p) 1,434,429. 
Chlor 
XXIV. (m) 619,549; 625,159. 
Trimethyl 
XXIV. (m) 1,338,297. 
Acid: 


anhydrides, Organic 
XXII. 1,326,040. 

chlorides, Organic 
XXII. 1,326,040. 


Acridin: 


Amino tolu naphth 
I. 643,569. 
Diamino 
XXII. 1,410,494. 
3.6-Diamino N-methyl 
‘ I. 1,427,431; 15427,432- 
XXIV. (m) 1,408,974. 


2-7-Dimethyl, dimethyl 3-amino, 6-amino 


I. 1,473,660. |. . 
Tetramethyl 2.7-diamino, disulfate 


1,418,852. 


Aerylie acid, 2-Nitro phenyl oxy: 
VII. 227,470; 228,300; 233,459. 
Adipie acid: 
LE. 9383565: 


497 


Aleohol: 
Lit, 25,300: 
XXII. 1,302,011; 1,311,824; 1,315,619; 
sesego) 1,425,625; 1,427,215; 
1,437,483. 
XXIV. One ahs 
Aldehyde: 
ITT) -45204,6390. 
Alizarin: 


III. 186,032; 188,061; 258,530; 
446,893; 503,295; 772,857; 


826,509. 

XXII. 275,128. 
XXIV. (m) 966,820. 
4-Amino 

III. 569,405. 
Eek 

II. 569,404 
Blue 


III. 399,479; 399,480; 399,481; 
401,633; 527,457; 790,079. 
Bordeaux 
III. 476,418; 476,419; 476,420; 
476,491; 502,265; 608,238. 


Green 
IIT. 399,482; 401,635. 
2-Nitro 
III. 790,079. 
pentacyanin 
III. 603,659. 
Alkylation: 
XXII. 1,426,380; 1,429,714; 1,431,470; 
1,433,925. 
Alloxan: 
Anilin 
XXIV. (m) 676,859. 
Dimethyl 
XXIV. (m) 667,388. 
Allyl: 
alcohol 
XXIV. (m) 1,360,994. 
bromide 


XXIV. (m) 1,336,952; 1,415,700. 
1-Amino 5-Naphthol: 
VI. 729,601. 
1-Amino 5-or 8-Naphthol: 
VI. 1,029,639. 
1-Amino 7-Naphthol: 
VI. 727,963; 874,968; 1,411,245. 
t-Amino 8-Naphthol: 
VIL 535)381; 524,665. 
OV Olt, Ola. 
2-Amino 6-Naphthol: 
VI. 727,967. 
2-Amino 7-Naphthol: 
VI. 656,619; 924,231. 
2-Amino 8-Naphthol: 
III. 644,333; 687,171. 
1-Amino 2-Naphthol, ethyl ether: 
WViIs) 11-550;656. 
1-Amino 7-Naphthol, Acetyl: 
VI. 1,078,925. 
1-Amino 8-Naphthol: 
Acetyl 3.6-disulfo 
VI. 1,034,898; 1,114,771. 
Acetyl, 4.6-disulfo 
VI. 916,323; 1,127,261- 
Acetyl, 4-sulfo 
Its 4085207- 
2-Amino 5 Naphthol: 


Acetyl, 7-sulfo 
VI. 666,867; 941,088; 1,005,233. 


4’-Amino 1/2/-azimino phenyl, 7-sulfo 


Vii or6,161- 


583,635; 585,104; 591,616; 
608,999; 611,597; 611,664; 
618,963; 620,368; 620,369; 
627,679; 627,783; 628,233; 


498 DIGEST OF PATENTS 
3’-Amino benzoyl, 1.7-disulfo 
VI. 889,016. 
1-Amino 8-Naphthol, 3/-Amino benzoyl, 
4-sulfo: 


Vii a51 83,835. 
2-Amino 5-Naphthol: 
3’-Amino benzoyl, 7-sulfo 
VI. 724,078; 1,185,413; 1,265,031; 
1,282,354; 1,292,385; 1,342,134; 
1,362,936; 1,365,706. 
4’-Amino benzoyl, 7-sulfo 
VI. 888,837; 1,015,375; 1,022,287; 
1,022,288; 1,032,797; 1,041,146; 
1,065,950; 1,101,739; 1,150,675. 


3”-Amino benzoyl 3/-amino benzoyl, 7-sulfo 


VI. 993,073. 
2-Amino 8-Naphthol: 
4'-Amino benzoyl, 6-sulfo: 
VI. 1,065,950. 
4’-Anisidyl, 6-sulfo 
VI. 982,954. 
2-Amino 3-Naphthol, Benzoyl: 
VI. 1,145,072. 
6-Amino 1-Naphthol, Benzoyl 5.5’-dioxy 
2.2/-dinaphthyl urea: 
VII. 1,144,577. 
1-Amino 8-Naphthol: 
Benzoyl, 4.6-disulfo 
VI. 1,073,902; 1,073,903; 1,073,904; 
1,073,905. 
Benzoyl, 4-sulfo 
524,220. 
2-Amino 5-Naphthol, Benzoyl, 7-sulfo: 
VI. 679,974; 931,423; 931,424; 
1,027,148. 
1-Amino 2-Naphthol, Brom, 4-sulfo: 
VI. 1,014,039. 
1-Amino 7-Naphthol, 2/-Chlor benzoyl: 
VI. 1,188,545. 
1-Amino 2-Naphthol, Chlor, 4-sulfo: 
MIT. 4,026;5257. 
Amino 5-Naphthol: 
1.2-Di-, 7-sulfo 
VI. Serianee 813,155; 873,798; 


886,9 
sig” ane een 1.2-di-, 7-sulfo 
VI. 8395155, 


2-Amino 8-Naphthol, Dialkyl, 6-sulfo: 
VI. 567,413. 


1-Amino 8-Naphthol, 2’.4’-Dichlor benzoyl, 


4.6-disulfo: 
VI. - 1,073,951. 
Amino Naphthol disulfo: 
VI. 501,500. 
1-Amino 2-Naphthol 3.6-disulfo: 
VI. 521,985; 778,476. 
XII. 808,919. 
1-Amino 2-Naphthol 4.6-disulfo: 
XII. 808,919. 
1-Amino 8-Naphthol: 
2.4-disulfo 
VI. 539,609; 560,449; 603,645; 
683,119; 999,558; 1,426,190. 
XV. 614,538; 673,388. 
3.5-disulfo, ‘*B” 
VI. 606,436; 606,438; 
3.6-disulfo, “HH” 
VI. 462,415; 464,135; 468,040; 
480,326; 482,106; 496,392; 
498,759; 498,873; 498,874; 
499,198; 509,625; 512,493; 
514,599; 514,931; 516,203; 
521,986; 533,508; 541,750; 
542,073; 544,699; 544,700; 
55794353 557,436; 557438; 
557439; 558,613; 561,694; 
561,709; 563,384; 563,386; 
576,511; 57957733 583,634; 


606,439. 


639,040; 646,711; 652,456; 
655,013; 666,866; 670,398; 
684,065; 688,478; 717,550; 
728,477; 792,033; 792,034; 
843,808; 877,644; 932,813; 
950,404; 950,405; 964,786; 
987,417; 988,000; 1,014,982; 
1,014,983; 1,023,120; 1,028,306; 
1,052,262; 1,126,489; 1,199,233; 
Aa 1,259,499; 1,263,030; 
383,711. 
4.6-disulfo, Kh 
VI. 563,383; 563,385; 563,386; 
06,181; 606,204; 611,597; 
613,638; 613,639; 613,640; 
613,641; 613,642; 613,645; 
936,456; 969,450; 1,006,051; 
1,128,814. 
XXIV. (m) 1,308,071. 
1-Amino 8-Naphthol 4 or 5.7-disulfo: 
VI. 671,896. 
2-Amino 1-Naphthol: 
3.6-disulfo 


4.8-disulfo 
XII. 808,919. 
2-Amino s5-Naphthol 1.7-disulfo: 
VI. 532,479; 759,613; 763,761; 
897,529; 933,448. 
2-Amino 8-Naphthol 3.6-disulfo: 
VI. 516,604; 556,164; 556,298; 
560,448; 578,432; 601,033; 
601,859; 608,024; 1,076,756. 
1-Amino 8-Naphthol: 
Ditolyl sulf-,3.6-disulfo 
VI. 640,989. 
Ethyl, 3.6-disulfo 
7975732. 
1-Amino 7-Naphthol, Methyl: 
VI. 874,067. 
1-Amino 2-Naphthol, Phenyl: 
XXII. 1,460,774. 
2-Amino 5-Naphthol: 
Phenyl amino acetyl, 7-sulfo 
VI. 1,092,842. 
Phenyl, 7-sulfo 
VI. 682,510; 843,137; 843,149; 
843,736; 860,220; 860,221; 
877,643; 933.447; 933,562; 
935,031; 963,739; 1,009,741; 
1,020,756; 1,049,109; 1,079,415. 
2-Amino 8-Naphthol, Phenyl, 6-sulfo: 
VI. 953,033; 953,034; 982,952; 
982,953; 993,020; 995,161; 
1,045,196; 1,076,321; 1,077,492. 
2-Amino s5-Naphthol, 4’-Sulfamino benzoyl, 
7-sulfo: 
VI. 1,098,388. 
1-Amino 8-Naphthol, sulfurus acid ester: 
VI. 897,529; 898,217; 912,356. 
Amino Naphthol sulfo: 
VI. 442,369, 560,448. 
1-Amino 2-Naphthol 4-sulfo: 
VI. 790,363; 790,364; 805,198; 
806,415; 807,422; 835,539; 
839,489; 958,912; 1,014,114; 
1,023,199; 1,233,433; 1,237,183; 
1,402,350; 1,437,758. 
XII. 808,919. 
1- Amino 2-Naphthol Gentian 
VI. 1,160,344. 
XII. 808,919. 
1-Amino 2-Naphthol 6-sulfo, ethyl ether: 
VI. 1,150,675. 


INTERMEDIATE INDEX 


1-Amino 2-Naphthol 7-sulfo: 


XII. 808,910. 


1-Amino 5-Naphthol 7-sulfo: 

VI. 558,344; 654,064; 1,101,739. 
1-Amino 6-Naphthol 3-sulfo: 

VI. 1,009,797; 1,052,135. 
1-Amino 7-Naphthol 4-sulfo: 


VI. 727,966; 


899,171. 


1-Amino 8-Naphthol: 


509,929; 
54357475 
509,088; 
610,349; 
683,120; 
932,812; 


1,009,745; 


524,220; 
543,748; 
593,790; 
638,127; 
692,675; 
958,830; 
1,188,4213 


1,363,886; 1,372,439; 1,415,704. 


4-sulfo 
VI. 506,284; 
533,508; 
578,432; 
603,008; 
644,334; 
88,036; 
974,346; 

5-sulfo 
VI. 615,497; 


5 or 4-sulfo 
VI. 682,510. 


958,774. 


2-Amino 1-Naphthol;: 


4-sulfo 

XII. 808,919. 
5-sulfo 

XII. 808,919. 


2-Amino 3-Naphthol 7-sulfo: 


VI. 


2-Amino 5-Naphthol: 


sulfo 
VI. 
1-sulfo 
VI. 
7-sulfo 
VI. 521,095; 
59353473 
662,122; 
678,323; 
724,893; 
740,768; 
832,393; 
859,930; 
808,217; 
982,507; 


1,012,619; 


1,210,751. 


1,026,902. 


521,096; 
624,256; 
663,498; 
697,765; 
724,894; 
763,761; 
839,360; 
877,644; 
941,088; 


1,088,735; 1,338,414. 


55553593 
658,897; 
673,079; 
709,186; 
740,767; 
767,070; 
839,382; 
888,837; 
969,450; 


1,006,929; 1,009,796; 


1,014,633; 


1,024,308; 


4Amino Naphthol sulfo: 
VI. 512,167. 
2-Amino 8-Naphthol: 
eet 6-sulfo 
- 1,043,873. 
3-Xylyl 6-sulfo 


499 


1,024,794; 
1,079,415; 
1,126,656; 
1,160,406; 
1,263,030; 
XIV. 951,047. 


1,032,797; 
1,092,842; 
1,150,825; 
1,213,075; 
1,319,852; 


2-Amino 8-Naphthol: 


6-sulfo, ‘*G”’ 


1,074,429; 
1,113,468; 
1,159,3753 
1,216,760; 
1,378,388. 


VI. 454,648; 
501,500; 
526,763; 
536,431; 
536,880; 
557.4393 
571,933; 
595,021; 
602,855; 
613,641; 
620,574; 
639,041; 
644,462; 
654,167; 
672,714; 
683,190; 
842,048; 
945,780; 
Q71I,112; 


491,410; 
525,245; 
533,463; 
536,878; 
556,164; 
560,448; 
575,904; 
599,532; 
606,204; 
613,646; 
622,961; 
644,291; 
647,237; 
666,866; 
676,494; 
748,076; 
858,444; 
963,7393 
982,508; 


501,160; 
525,626; 
535,036; 
536,879; 
5574373 
560,449; 
578,580; 
601,033; 
(ob segs Oe Ge 
619,503 
629,748; 
644,292; 
654,065; 
671,543; 
679,221; 
832,393; 
921,239; 
971,111; 
989,000; 


VI. 982,955. 
Amins: 
Aromatic 
III. 659,565; 666,594; 666,702; 
669,894; 675,572; 687,657; 
688,576; 723,125; 734,325; 
734,866; 748,375; 749,913; 
812,599; 996,487. 
ie 211,180. , 
» 350,230; 455,952; 951,046. 
XXII. 1,394,851. Rai aay 
Carboxylic 
XIV. 350,230. 
Heterocyclic 
XIV. 951,048. 
Nitroso-secondary 
420,311. 


Nitroso-tertiary 
XM. 420,311. 


Sulfo 
XIV. 350,230. 
Amyl alcohol: 
XXIV. (m) 1,352,082. 
Anilid: 
Amino stearic acid 
902,021. 
4-Amino stearic acid 
VII. 879,424. 
2-Nitro benzyl form- (See Benzyl 
manilid, 2-Nitro) 
bis=3’-Oxy 
XXII. 1,315,127. 
Stearic acid 
VI. 879,424. 
Anilin: 
II. 38,589 Re. 4,746; Re. 4,747; 
79,942 Re. 3,103; 96,242; 
111,654 Re. 7,429; Re. 7,430; 
Re. 7,431; Re. 7,432; 138,155; 
189,538; 193,158; 387,007; 
7 bese eM i 


III. 599,425; 623,638; 631,605; 
631,606; 631,613; 632,621; 
647,370; 659,565; 659,566; 
668,445; 669,894; 688,576; 
748,375; 754,264; 793,558; 
809,894; 996,487; 1,015,329; 
1,238,932; 1,280,648; 1,394,851. 
2Prr.O7 rs 22t, TTA so22r. Lies 


VI. 


for- 


22. Ul 7 2elolios 
221,120; 247,601; 
251,162; 253,598; 
310,155; 333,039; 
409,384; 421,640; 
480,326; 485,283; 
498,405; 516,756; 
524,251; 524,665; 
562,200; 563,383; 
606,438; 613,638; 
613,643; 619,194; 
640,989; 656,621; 
663,498; 673,079; 
717,550; 722,860; 
806,077; 843,808; 
902,021; 902,186; 


993,073; 999,230; 1,026,902; 


221,119; 
242,707; 
269,359; 
333,041; 
431,297; 
498,404; 
516,757; 
5571440; 
59353473 
613,639; 
622,961; 
662,122; 
688,478; 
724,078; 
888,837; 
944,328; 


1,000,606; 
1,024,080; 
1,082,581; 
1,154,826; 
1,201,544; 
1,365,040; 
1,416,621; 
XIV. 951,047. 
6 or 7 sulfo 
VI. 1,099,676. 


1,009,741; 
1,024,081; 
1,123,430; 
1,173,077; 
1,270,290; 
1,371,979; 
1,429,781. 


1,014,984; 
1,056,493; 
1,126,466; 
1,199,2343 
1,359,969; 
1,408,405; 


1,028,239; 1,042,198; 1,078,503; 
1,126,489; 1,206,232; 1,286,411; 
1,447,485. 

620,562; 622,139; 647,279; 
712,190; 776,884; 818,341; 
841,456; 868,294; 868,755; 
894,149; 894,579; 1,243,170; 
1,442,743; 1,467,598. 

666,627. 

613,911; 951,047. 


VII. 


IX. 
XIV. 


500 DIGEST OF PATENTS 


XV. 629,221; 630,952; 641,587; 
Apel TSS 785,075. : 
796,443; 1,128,368; 1,329,808. 
XVIII. 32,065; 50,3353; 53,241; 248,154; 
252,202; 283,766; 310,128; 
471,638; 707,813; 1,042,493; 
1,065,405. 
XIX. 516,580; 551,885; 646,794. 
XXII. 1,303,624; 1,422,494; 1,460,774. 
XXIII. (Ab) 1,277,056; 1,350,600. 
XXIV. (e) 1,401,631; (m) 615,829; 
709,321; 741,585; 1,197,462; 
1,405,228; (pl) 1,422,506; 
1,477,805. 

Alkyl 


XXII. 1,413,494. 
4-Amino 3-chlor dimethyl 
VI. 891,931. 
3-Amino dimethyl 
I. 1,255,739; 1,255,740; 1,455,486; 
. 1,455,487. 
4-Amino dimethyl 
PES r, 105; 501. 
3-3/-Azoxy di- 
VIP 763,701 5 91,305,700. 
Benzyl ethyl, sulfo 
XVIII. 866,359. 
Benzyl methyl 
XV. 1,449,681. 
XVIII. 611,628; 684,367. 
Benzyl methyl, sulfo 
XVIII. 464,538. 
Benzyl sulfo 
I. 726,688. 


VI. 655,013; 906,422; 982,954; 
987,417; 1,014,982; 1,051,565; 
1,076,819. 

VII. 916,030. 

XII. 982,050; 988,870. 


1,073,951. 


HIIs *1,002)066; 1,025,147. 

VI. 752,562; 789,096; 959,078; 
987,417; 1,014,982; 1,014,983; 
1,028,306. 

2-Chlor, 5-carbo 

VI. 942,916. 

2-Chlor methyl 

XV. 841,877. 

3-Chlor 4-nitroso dimethyl 

VI. 891,931. 

4-Chlor, 3-sulfo 

VI. 984,900. 


VI. 297,852. 
XVIII. 297,415; 297,416; 498,471. 
2.5-Dichlor 
VI. 627,679; 652,456; 879,053; 
932,813; 950,405; 1,003,295; 
1,457,114. 
3.4-Dichlor 
VI. 787,768; 830,312; 1,010,930. 
2.5-Dichlor, 4- ‘sulfo 
VI. 949,633; 1,150,675. 
3.4-Dichlor, 5-sulfo 
VI. 787,767. 
3.4-Dichlor, 6-sulfo 
VI. 830,312; 849,739. 
4. pret 2-sulfo 
I 


1,270,290. 

Diethyl 

VI. 297,852; 313,118. 

XVIII. 290,893; 325,827; 329,637; 
412,613; 412,614; 412,615; 
1,478,015. 

Dimethyl 

VI. 297,852. 

XXIV. (m) 922,995. 

XVIII. 222,257; 263,420; 290,856; 
290,891; 290,892; 310,128; 
325,828; 329,030; 464,538; 
519,971; 564,801; 709,160; 


2-Anisidin: ES 


4-Anisidin 3-sulfo: 


: 1,402,195; 1,470,554; 1,470,555. 
peeulre 

I. 974,346. 
Ethyl 


« 4205s res 

VILs (657665, 

XV. 1,140,745. 
Ethyl benzyl 
XVIII. 623,346; 668,580. 
Ethyl benzyl, disulfo 
XVIII. 501,069. 
Ethyl benzyl, sulfo 


380,008. 
Vi eat, 253.0754 


XIX. 641,184. 

Methyl, w-sulfo 
VI. 1,027,148. 

2-Nitro benzyl 
XXIV. (m) 428,286. 
Nitro benzyl, sulfo 
XXII. 648,261. 
Nitroso diethyl 


<i 898,842. 
Nitroso dimethyl 
VII. ioe 


X. 
XXIV. a Taieooe (pl) 1,418,771; 
(pl) 1,443,381. 
Nitroso methyl ethyl 
Xo 420,32. 
Oxy alkyl 
XXII 778,772: 
3-Oxy dimethyl 
- 933,841. 

Oxy vite 
VIL. - 772,775. 
N-Oxy ethyl benzyl 
XVIII. 1,478,039. 


2-sulfo 
VI. 933,446; 933,448; 978,580; 
1,154,826 
3-sulfo 


VI. 1,405,687. 
Thio, disulfo 


VI. 880,293. 
3.4.6- Trichlor 
-VI. 786,767. 


Trimethyl ammonium 
VI. 1,028,140; 1,029,639. 


2-Anisidin: 


VI. 213,563; 213,564; 512,116; 
675,629; 935,016; 935,017; 
1,052,262; 1,073,904; 1,365,040. 

XXIII. (Az) 1,099,108. 
XXIV. (f) 489,728. 


4-Anisidin: 


XVIII. | i ri2zr7,238: 
Aceto acet 
VI. 1,076,819. 


Anisidin: 


4-Amino d 
II. 992,947; 1,105,554. ie 
5-Amino 4-chlor acetyl 
VI. 1,000,269. 
4-Amino 5- “chlor oxalyl 
VI, 3,010,433. 
5-Amino 4-chlor oxalyl 
Vie ei,032482. B 


4-Nitro ie 

VI. 982,952; 1,145,072. x 
5-Nitro se 
VI. 945,780; 1,051,565. 


VI. 770,430. 


XXIV. (e) 1,325,168. 
4-Acetyl amino, 5-carbo 


INTERMEDIATE INDEX 501 


VII. 881,158. 
Acetyl 2.4-diamino 
VI. 920,151. 
4-Amino 
XXIV. (m) 295,825. 
2.4-Diamino (See Anisidin, 4-Amino) 


2-Nitro 

XXII. 1,469,586. 
4-Nitro 

XXIV. (m) 295,825. 


Nitro chlor 
II. 695,812. 
Nitro 3-diamino 
Li e1,105,447- » 


Anisoyl Chloride, 3-Nitro: 
XXIV.. (m) 1,317,250. 
Anthracene: 

III. 95,465 Re. 4,320; Re. 4,321; 
97,597 Re. 4,558; 127,426; 
153,536; 154,153; 787,859; 
922,282. 

126,277; 130,909; 131,393; 
184,142; 227,588; 685,895; 
1,083,051; 1,103,383; 1,303,168; 
1,303,639; 1,326,515; 1,355,098; 
1,374,721; 1,404,055; 1,409,897; 
1,417,367; 1,419,186; 1,444,068; 
1,455,448; 1,456,848; 1,466,683; 
1,467,258. 


XXII. 


III. 1,042,931. 


III. 654,505; 654,506. 
1.9-dicarbo acid imid 

Dee 210,134. 

MEDIY 1.263.262. 
1.9-dicarbo acid anhydride 


III. 1,422,889. 
g.10-Dihydro 

TDI, 1st 52: 
9.10-Dinitro 

TALS 91,150,152: 


Anthrachrysone: 
III. 511,901; 569,419; 727,389. 
AXIT. 871,507. 
Dinitro, disulfo 
III. 555,904; 569,418. 


Anthradiquinone: 
III. 506,265. 


y: 
Rit 290,139: 


Anthraflavie acid: 
III. 648,271; 826,510. 
Dinitro disulfo 
III. 996,487. 


Anthraflavin : 
iit. 656,463. 
1-Anthraisothiazole, 4-Amino, 8-sulfo: 
TI; 1,076,249: 
Anthranilie acid: 
III. 961,047; 961,048; 998,772; 
1,008,906; 1,058,604; 1,086,123. 
VI. 737,445; 757,109; 837,128; 
1,159,375}; 1,270,325; 1,323,285; 
1,338,506. 
VII. 643,502; 661,871; 662,754; 
662,755; 699,581; 768,455; 
877,702; 1,322,052. 
XIV. 951,047. 
XXII. 661,821; 690,325; 765,576; 
993,915. 
XXIV. (f) 658,769. 
ethyl ester 
III. 662,703. 
Acet 4-amino 
VII. 867,306; 872,085. 
Acet 5-amino 
VII. 872,086; 881,157. 
4-Amino 1-anthraquinonyl 


III. 998,772. 


5-Brom 
XXII. 1,003,289. 

4-Chlor 
Til, %x,207,081. 

5-Chlor 


VI. 1,149,231. 
Cyan methyl 
VII. 662,754; 662,755; 730,148; 
761,007. 
Dichlor acet 
VII. 867,679. 
4-Ethoxy acetyl 
VII. 867,305. 
sree thio 


rr £008,457. 
Methyl 

VII. 722,793. 
4-sulfo 


XII. 731,670. 
Anthranol: 
III. 999,680; 1,046,498; 1,052,520. 
XXII. 795,751; 1,293,610. : 
5-Anthranol, 1-Amino: 
III. 975,863. 
Anthranol, a-Oxy: 
VIF. 1,025,174. 
Anthrapurpurin: 
XXIV. (m) 678,070. 
Anthrapyridone: 
4-Amino 2-methyl 

III. 031,618. 

3’-Chlor phenyl 4-amino N-methyl 

III. 995,306. 

Phenyl 4-amino N-methyl 
III. 994,803. 
Anthraquinone: 

III. 95,465; 446,892; 496,139; 
874,743; 885,557; 1,014,204; 
1,036,880; 1,036,881; 1,044,933. 

XXII. 275,128; 743,664; 755,801; 
851,423; 999,062; 1,293,610; 
1,324,716; 1,375,972; 1,404,056; 
1,420,198; 1,429,514; 1,444,068; 
1,455,448; 1,461,745; 1,466,683; 
1,467,258; 1,474,507. 

Acetyl amino 

III. 1,266,896. 

Acetyl 1-amino 

III. 863,401; 925,917. 

Acetyl methyl 1-amino 4-brom 

III. 875,390. 

acridone 

III. 1,008,908. 

2-aldehyde 

TLDs 080,224) 1,162,400 else 557-20+ 

1-Amino 

DIS Vrig10s8 800;80sn oll, 47a: 
814,137; 855,248; 860,480; 
876,190; 929,443; 935,827; 
935,878; 938,565; 938,566; 
957,041; 957,125; 960,182; 
986,521; 993,736; 995,936; 
1,016,604; 1,037,410; 1,050,829; 
1,070,196; 1,090,636; 1,095,780; 
1,216,021 3" 1,285,727. 

Vie 7615123: 

XIV. 1,437,783. 

2-Amino 

III. 682,523; 724,789; 739,145; 
739,579; 785,122; 786,085; 
809,892; 909,800; 958,325; 
993,992; 1,016,638; 1,025,195; 
1,026,588; 1,038,003; 1,042,931; 
1,062,988; 1,095,731; 1,121,026; 
1,451,270; 1,459,536; 1,478,061. 

XXII. 1,028,521; 1,452,774. 

4-Amino, 1.2-acridone 

III. 1,002,270; 1,047,940. 

1-Amino, 2-aldehyde 

III. 1,285,727. 

Alphyl 1- or 2-amino 


502 DIGEST OF PATENTS 


III. 675,574. 
1-Amino 2-brom 

III. 985,352; 1,076,329. 
nee 1-brom 3-chlor 

iii 52,774 
MXIT. 1,452,774. 
1-Amino 4-brom, 2-sulfo 

TTD ert 31.576: 
4-Amino 1-brom, 3-sulfo 

III. 1,207,981. 
1-Amino 4-chlor 

III. 1,078,505. 
1-Amino 5-chlor 

LIT O71, 2252 
1-Amino 6 or 7-chlor 

III. 961,612. 
2-Amino 3-chlor 
AXAII. 3,452,774: 
1-Amino, dibromid 

III. 654,294. 
2-Amino 1.3-dibrom 

III. 994,756. 
1-Amino 2-ethoxy 4-brom 

III. 1,139,540. 
2-Amino, mercaptan 

TII. 1,126,475; 1,459,536. 
2-Amino, 1-mercaptan 

III. 1,032,216. 
1-Amino 4-methoxy 

III. 950,343; 950,344; 957,039. 
4-Amino 1-methoxy 

III. 950,344. 
1-Amino 2-methyl 

III. 688,645; 690,292; 915,385; 

1,285,726. 

XV. 1,129,574; 1,129,575. 
XXII. 845,129; 1,394,851. 
2-Amino 3-methyl 

III. 992,567. 
1-Amino 4-oxy 

III. 675,572; 957,146. 
1-Amino 5-oxy 

III. 748,375. 
4-Amino 1-oxy 3-brom 

III. 801,418. 
6-Amino, 1.2-phenyl thiazole 

XV. 996,485. 
1-Amino, 5-sulfo 

XV. 961,387. 
2-Amino, sulfo 

III. 692,762. 
2-Amino, 3-sulfo 

VI. 1,028,139. 
2-Anilino 

III. 1,280,648. 
1-Anilino 2-methyl 

CLT y 133,081. 
1-Anilino, sulfo 

III. 753,657. ; 
1-Anthraquinonyl 4-amino, 1.2-acridone 

III. 1,047,940. 
2'-Anthraquinonyl 1.4-diamino 

III. 928,891. 

Benzoyl 1-amino 4-amino 

III. 971,224; 971,225; 993,735. 
Benzoyl 1-amino 2-brom 

1,001,408. 
Benzoyl 1-amino 4-chlor 

III. 971,224; 1,044,603. 
Benzoyl 1-amino 6-chlor 

III. 986,521. 

Benzoyl 4-amino 1-chlor 

III. 996,109. 

Benzoyl 5-amino 2-chlor 

AVA Terr sto. 
Benzylidin 2.6-diamino 

V. 996,485. | 
Brominated, 1.2-acridone 

III. 1,050,829. 
Brom t-amino, sulfo 

III. 666,594; 734,866. 
1-carbo 

TLL, r,002,325. 
2-carbo 


III. 878. 

1-Chlor sei” 

III. 943,717; 960,182; 999,785; 
9991798: 1,002,270; 1,008,906; 
1,023,847; 1,047,940; 1,123,390. 

XXII. 993,915. he 
2-Chlor 

III. 809,894; 814,137; 818,336; 
860,480; 863,397; 928,891; 
931,618; 950,343; 1,105,004; 
1,446,163. 

XV." 2,528,140; 

1-Chlor acetyl 2-amino 
III. 1,126,475. 
Chlor, acridone 

III. 1,052,507. 

1-Chlor, 2-aldehyde 

III. 1,004,433; 1,047,812. 

1-Chlor 4-amino 

III. 1,007,104. 

1-Chlor 5-amino 

III. 999,785. 

4-Chlor 1-amino 2-methyl 

III. 831,002. 

2’-Chlor benzoyl 2-amino 

Ill, 1,087,243: 

1-Chlor, 2-carbo 

III. 1,002,066; 1,010,930; 1,011,968; 
1,018,837; 1,044,673; 1,044,674; 
1,044,675; 1,067,046; 1,090,636. 

4’-Chlor 2/-carbo 4-anilino 1-amino 3-sulfo 

ITI. 1,207,981. 

s’-Chlor 2/-carbo phenyl 1-anilino 
III. 1,023,847. 

4-Chlor 2-methyl 
III. 932,290. 

1-Chlor 2-oxy 
III. 1,087,293. 

1.2-Diamino 

III. 1,062,975; 1,079,568. 

1.3-Diamino 

ITI. 619,574. 

1.4-Diamino 

III. 943,717; 957,042; 996,109. 

1.5-Diamino 

III. 621,679; 632,621; 640,086; 
643,451; 648,332; 673,691; 
704,798; 707,374; 713,432; 
738,614; 767,259; 791,869; 
863,397; 938,618; 999,798; 
1,105,004. 

XXII. 631,607; 631,608. 
1.8-Diamino 

III. 938,619. 

1.4-Diamino 2.3-dibrom 

III. 775,367; 785,123. 

1.4-Diamino 2.3-dichlor 

III. 1,038,589. 

2.6-Diamino, 1.5-dimercaptan 

III. 1,090,621. 

1.5-Diamino 8-oxy 

III. 935,781. 

1.5-Dianilino 

III. 648,331. 

1.3-Dibrom 2-amino 

III. 775,369; 785,121; 808,762. 

1.5-Dibrom or dinitro dimethyl 4.8-diamino 

JEL), 687,657. 

1.2-Dichlor 

TI. 1,032,2153) r,0g2,2160 

1.5-Dichlor 

III. 061,048; 1,044,602; 1,065,102. 

2.7-Dichlor 

III. 950,344. 

1.5-Dichlor 4.8-dinitro 
III. 675,573. 
Dichlor 2-methyl 

LIL. 9 2,0625075. 

w-Dichlor methyl 

III. 902,895. 

w-Dichlor 2-methyl 
XXII. 828,741. 
1.4-Dichlor, a-sulfo 


XXII. 1,442,491. 
0 UE Ea hae dinitro 
753573:- 

N-Dihydro 1.2.2’.1’, azin 

IT. 15317,160. 
1.2-dimercaptan 

Pie t.032,20 5. 
1.5-dimercaptan 

JIT.” 1£3028,637- 

AV. 961,388. 
Dinitro 


INTERMEDIATE INDEX 503 


III. 519,229; 650,756; 654,505; 


654,506. 
1.2-Dinitro 

III. 500,917. 
1.4-Dinitro 

III. 502,603. 
1.5-Dinitro 


III. 617,886; 617,981; 631,605; 


659,565; 659,566; 

XV. 597,983; 999,045. 
XXII. 631,606 
1.8-Dinitro 

Ill. 707,374. 
1.3-Dinitro 2-oxy 

III. 686,356. 
Dioxy, quinolin 

III. 790,079. 
a.a-disulfo 
XXII. 742,910; 1,437,571. 
1.5-disulfo 
ASL. 765,201. 
1.8-disulfo 
XXII. 765,637. 
2.6-disulfo 

III. 847,078. 

Vi. ot, 201,304. 
1.2.5.6-dithioxanthone 

Dies. 026,62 1. 
1.4-Ditoluidino 8-oxy, 7-sulfo 

III. 812,684. 
Erythroxy 

III. 666,702. 
Halogen 

EUS 1,026,027. 
Halogen amino, sulfo 

Ill. 707,373. 
Halogen 2-methyl 

Ill. 856,811. 
Hexaoxy 

III. 502,765; 868,399. 
Hexaoxy, disulfo 

III. 1,090,123. 
2-hydrazin 

III. 1,047,812. 
1-Iodo 2-methyl 
XXII. 828,778. 
I-mercaptan 

Tile 1,050,403. 
2-mercaptan 


III. 1,044,602; 1,044,603; 1,076,329. 


Methoxy, sulfo 
III. 778,036. 


1,417,875. 


y 
III. 715,662; 836,220; 837,840. 


XV. 899,845; 966,478; 
XXII. 803,507. 
Methyl 1-amino 
III. 853,041; 874,744. 
Methyl 1-amino 2-brom 
III. 985,352. 
Methyl 4-amino 1-brom 
III. 998,156. 
Methyl 1-amino 4-chlor 
III. 687,658. 

Methyl 1-amino 6-chlor 
III. 929,443. : 
Methyl 2-amino 1.3-dibrom 

III. 994,756. 
Methyl 1-amino 2-methyl 
III. 764,837. 


1,440,833. 


Methyl 1-amino 4’-tolyl 4-amino 


PEs 1,004,107. 
1-Methyl 2-brom 


III. 775,368. 
pis 

Lit. 723,125. 
1-Nitro 


IIT. 654,295; 961,047. 
1-Nitro amino 
XXII. 1,066,777. 
1-Nitro 4-amino 

III. 928,891. 
4’-Nitro benzoyl 1-amino 

III. 989,602. 
5-Nitro 1.4-diamino 

III. 1,045,805. 
Nitro methyl 

III. 764,837. 
1-Nitro 2-methyl 

III. 1,417,875. 
1-Nitro 2-oxy 
XXII. 722,719. 
4-Nitro 1-oxy, 2-sulfo 

III. 666,702. 
Nitro, sulfo 

III. 656,081. 
1-Nitro, sulfo 

III. 688,576. 
1-Nitro, 5-sulfo acid 

Ill. 778,036. 
Oxy and sulfoxy 
XXII. 1,465,689. 
1-Oxy : 
TIT. 793,558; 1,010,463; 1,028,637. 

XIV. 868,399. 
XXIF. 1,401,125. 
1-Oxy 2.4-diamino 

III. 1,034,895; 1,034,896. 
1-Oxy 2-methyl 4-chlor 

III. 1,062,990. 


XXIT. 1,465,689. 
Phenanthridone 

III. 1,001,408. 
rks amino 2-methyl 


Il 916,154. 
1-sulfo 
III. 778,670. 
XXII. 757,057; 757,058; 1,442,491. 
2-sulfo 


III. 754,264; 763,233; 779,825; 
1,026,557; 1,036,880 
XXII. 1,104,943; 1,238,932; 1,338,363; 
1,338,364; 1,340,603. 


XXII. 746,405. 
1.2.5.8-Tetraoxy 
III. 476,418; 476,419; 476,420; 
476,491; 608,338; 734,325. 
1.4.5.8-Tetraoxy 
III. 754,768. 
Tetraoxy, disulfo 
III. 648,271. 
1-Toluidino 2-amino 3-brom 
III. 1,065,440. 
1-Toluidino 2’.4-dioxy 
III. 729,073. 
1-Toluidino 2-oxy 
SOX 722.7 00; 
4-Tolyl, sulfo 


Ill. 675,574. 
4’-Tolyl 1-amino 2-amino 
III. 844,835. 


1.2.4-Triamino 
III. 957,040; 1,022,781; 1,023,248. 
1.4.5-Trioxy 
III. 778,036. 
1.4.8-Trioxy 
III. 812,599. 
2-Anthraquinonyl:, 
urea chloride 
III. 1,025,195. 
urethane 
III. 958,325. 
Anthrarufin: 
III. 595,349. 
Brom dinitro, sulfo 


504 DIGEST OF PATENTS 


III. 656,670; 656,730. 
4.8-Diamino 
III. 605,568; 656,668, 935,590. 
4.8-Diamino, disulfo 
III. 656,668; 658,514. 
Dinitro, disulfo 
III. 826,750. 
4.8-Dinitro, disulfo 
DTS 623-220) 
1.2-Anthrimidazole, 4-Amino phenyl: 
III. 1,022,781. 
a-Anthrol: 
VII. 961,396; 980,140; 985,767; 


985,768; 1,005,141; 1,101,778. 


Aromatic substances, Sulfo: 
XXII. 1,416,284. 
Aryl amins: 
Acetyl methyl 
XXII 154115683: 
2.3-Oxy naphthoic acid 
XXIII. (Az) 1,099,108. 
Sodium 
XXII. 903,588. 
Aurin: 
XVIII. 307,401; 316,471; 318,484; 
; 333,649. 
tricarbo acid 
XXIV. (m) 1,412,440. 
Barbiturie acid, Diethyl: 
XXIV. (m) 1,316,047. 
Benzaldehyde: 
MX VITIS 7,218,232, 
XIX. 624,877. 
XXII. 575,237; 613,460; 1,302,273; 
1,321,959; 1,405,261. 
XXIV. (f) 581,053; (m) 710,005; 
1,356,877. 


XXII. 640,564. 


807,119; 813,155; 873,798; 
886,985. 


VI. 583,634. 
XVIII. 248,153; 248,154. 
Amino, bisulfite 
VI. 999,230. 
arsonic acid 
XXIV (m) 
chlor derivatives 
XXII. 315,932. 


TUS s7, 2092485, 1,202,200. 
VII. 673,887. 
XVIII. 684,367; 877,053; 887,620; 
¥,L01,7703 01, 2495575: 
XIX. 738,227. 


XVIII. 995,404; 1,065,405. 
2-Chlor 3-amino 

V 980,251; 980,521. 
2-Chlor 5-amino 
XVIII. 999,028; 1,026,089. 
2-Chlor 4.6-dibrom 5-amino 

VIN 1,025.305- 
4-Chlor 2-nitro 

VII. 677,239: 
4’-Chlor 2/-nitro 3-phenoxy 2.6-dichlor 
XVIII. 1,044,836. 
2.4-Dibrom 3-oxy 
XVIII. 1,004,609. 
Dichlor 
XVIII. 525,627; 684,367. 
2.6-Dichlor 
XVIII. 877,054. 
2.6-Dichlor 5-amino 

Vireo 027 20404 1,02T- 300. 
4.5-Dichlor 2-nitro 

1,050,179. 

2.6-Dichlor 3-oxy 
XVIII. 1,004,610. 
3.4-Dimethyl 
XVIIT. 1,470,554; 1,470,555. 
Dimethyl 4-amino 
XXII. 667,382. 
2.4-disulfo 


XIX. 1,006,738. 
SLL. PSST eo: 
2.4 or 2.5-disulfo 
XXIII. 684,367. 


2.5-disulfo 
XVIII. 1,478,039. 
3-Methoxy 
XVIII. 412,615. 
Nitro 

XXII. 661,872. 
2-Nitro 


VII. 257,812; 257,813; 257.8143 
257,815; 540,427; 726,688. 
XXII. 575,237. 
2 and 4-Nitro 
XXII. 636,994; 650,332. 
3-Nitro 
XVIII. 412,613; 412,614; 422,018. 
4-Nitro 
AVIII: 248,153; 252,202; 352,203, 
2-Nitro 5-methyl 
VII. 1,412,038. 
4-Nitro, 2-sulfo 
XVIII. 623,346; 668,580. 
XIX. 573,299. 


XXII. 1,023,758. 

3-Oxy 

XVIII. 412,613; 472,091; 519,971; 
567,567; 1,478,015. 


4-Oxy 

XVIII. 950,359. 

Penta chlor 

XVIII. 998,139. 

2-sulfo 

XVIII. 564,801; 877,052. 
Benzal Violet: 

XVIII. 661,800. 


Benzanthrone: 


III. 795,393; 995,396; 1,478,027. 


XXII. 876,679; 1,365,024. 


Amino 

III. 893,412. 
Chlor 

III. 906,367. 
2-Chlor 

III. 818,336. 
1.5-Dichlor 

Ill. 1,086,123. 
Halogen 

III. 1,003,268. 
2-Methyl 


III. 1,044,797; 1,097,343. 
XV. 927,868. 
Nitro methyl 

XV. 1,054,888. 
quinolin, 1.2- 

DEE oSriAgt. 

Benzene: 

VII. 955,699. 

IX. 1,380,186; 1,396,001. 
XXII. 1,450,081; 1,466,991. 
XAITV. (Ce) 1,320,0767.37320:0775 

1,325,168; 1,370,067; 
1,380,185}; 1,417,368. 
Acetyl oxy azo ; 
XXIV. (p) 604,049. 
Amino azo 

VI. 253,598; 268,507; 314,939; 

333,0375 365,409; 610,367; 

644,334; 863,396. 

XV. 731,669; 1,251,368. 
XVIII. 319,646. 
4-Amino azo, 3.3’-dicarbo 

VI. 1,338,506. 
Amino azo, disulfo 

VI. 354,746; 1,087,428. 
Amino azo, sulfo 

VI. 224,927; 224,928; 233,645; 

246,472; 256,380; 256,401; 

260,242; 261,766; 262,620; 

268,505; 313,118; 931,423. 

XIV. 951,047. 
Amino azo, 4-sulfo 


— 
% 


INTERMEDIATE INDEX 


VI. 302,170; 611,663. 
2-Amino formyl 4-amino chlor 
oe 12555739. 
4-Amino 3’ -sulfo N-phenyl azimino 
VI. 1,043,873. 
Chlor 
III. 1,355,100. 
IX. 1,299,171. 
XXIII. (In) 1,448,251. 
Diacetenyl 
Vil. 251,671. 
1.2-Diamino 
Ill. 1,419,502. 
3.3/-Diamino azoxy 
VI. 880,016. 
1.3-Diamino 2-chlor, 5-sulfo 
VI. 1,008,907. 
2.6-Diamino 1-chlor, 4-sulfo 
VI. 798,098. 
1-Chlor 2.4-dinitro 
IX. 1,162,109. 
Diamino dioxy arseno 
XXIV. (m) 1,053,300; 1,059,983; 
1,330,288 
1.2-Dichlor 
III. 1,011,068. 
Vis 830,312. 
XXIV. (p) 1,421,860. 
Dinitro 
XI. 898,842. 
2.4-Dinitro 
IX. 1,059,571. 
o-Dinitro acetenyl 
VII. 251,500. 
Dinitro chlor 
VI. 879,552. 
SAIL. § 5,330,074. 
XXIV. (e) 1,398,998; 1,401, eve 
1.2-Dinitro 4-chlor 
644,959. 
1.3-Dinitro 4-chlor 
807,289. 
XV. 610,541. 
2.4-Dinitro chlor 


1,059,571; 1,162,109; 1,299,171. 


XV. 628,608; 628,609; 650,292; 
650,203; 651,077; 653,670; 
660,058; 660,067; 661,907; 
701,035; 764,733; 764,734; 

__,. 77535703 889,936. 
2.6-Dinitro chlor, 4-sulfo 
XVIII. 886,815. 
Dinitro 3-dichlor 

XV. 695,835. 

1.3-Dinitro 4.6-dichlor 

V. 735,775: 
2.6-Dinitro 1.4-dichlor 

XV. 658,055. 

4.6-Dinitro 1.3-dichlor 

XV. 650,326. 

XXII. 648,753; 648,754; 648,755; 
650,327. 
1.3-Dinitro 4.6-dithiocyan 

XV. 735:775. 

3.5-Dinitro 1.2.4-trichlor 

XV. 688,646. 

3-disulfo 

XXIV. (m) 748,101. 
Hydrazo 

MON Dis 1,405,732. 
3-Methoxy, sulfo acid 
XVIII. 615,485. 


1-Methyl 2-amino 4-isopropyl 5-amino 
XV 


-_ 1,314,928. 
1-Methyl 2-amino 4-isopropyl 5-nitro 


1,314,923. 


1-Methyl 2-amino 4- isopropyl, 5-sulfo 


3 4,027- 
1-Methyl 2-nitro 4-isopropyl 
XXII. 1,314,920. 
Methyl 3-nitro 4-isopropyl 
ok Vs (mM) 1,306,512. 


Nitro: (See Nitrobenzene and derivatives) 


2-Nitro acetenyl 


VII. 251,499; 251,671. 
2-Nitro 1-chlor 
XXII. 628,607. 
4-Nitro chlor 
IT) 800;735; 
4-Nitro chlor, 2-sulfo 
XV. 640,559; 657,768; 671,908. 
XXII. 641,100. 
Nitro 4-dichlor 
VI. 605,812. 
Nitro, sulfo chloride 
XXII. 578,839. 
Nitroso 
VII. 899,994. 
Oxy azo 
XV. 645,738; 702,369. 
sulfo aci 
XXII. 1,459,081. 
XXIV. (f) 1,372,434. 
sulfo stearic acid. 
XXII. 628,503. 
Tetramino disazo (Bismarck Brown) 
VI. 384,315; 384,316. 


Benzhydrol: 


XVIII. 290,891. 

Alkyl diamino 

XVIII.. 816,457. 

Dimethyl dibenzyl diamino 

XVIII. 615,485. 

Tetraethyl diamino 

XVIII. 647,834; 835,882. 

Tetramethyl diamino 

VI. 879,053. 

XVIII. 423,341; 476,413; 476,414; 
484,607; 496,435; 498,471; 
501,069; 501,104; 506,918; 
517,493; 538,027; 541,572; 
580,186; 580,187; 580,188; 
605,619; 611,628; 621,393; 
628,243; 630,224; 639,076; 
639,977; 647,260; 664,450; 
673,632; 676,555; 688,967; 
886,815; 891,888; 891,889. 


Benzidin: 


VI. 320,638; 326,639; 344,971; 
358,865; 361,404; 362,813; 
365,666; 365,667; 380,008; 
380,403; 381,471; 384,315; 
386,192; 394,425; 394,841; 
395,474; 396,204; 399,581; 
401,483; 404,331; 410,057; 
410,058; 412,148; 417,295; 
423,550; 423,970; 426,345; 
432,989; 440,639; 440,953; 
442,369; 447,303; 454,840; 
476,393; 479,515; 482,106; 
493,413; 493,564; 498,303; 
499,198; 501,160; 501,500; 
503,148; 509,625; 511,532; 
514,599; 514,931; 515,381; 
516,203; 516,468; 519,522; 
521,096; 525,626; 533,508; 
535,036; 539,699; 544,699; 
55513593 556,164; 557:4355 
557,436; 557,437; 557.438; 
557,439; 560,448; 561,700; 
563,385; 567,413; 571,933; 
5727233 576,511; 578,432; 
579,773; 582,958; 583,634; 
588,182; 588,183; 591,616; 
601,033; 602,858; 603,008; 
603,090; 603,645; 603,646; 
603,647; 603,648; 606,181; 
606,204; 606,439; 608,024; 
611,III; 613,640; 613,641; 
613,642; 613,643; 613,644; 
613,645; 622,961; 627,679; 
628,233; 631,610; 631,611; 
644,291; 644,292; 652,456; 
655,013; 656,619; 666,867; 
679,974; 688,478; 713,507; 
717,550; 718,389; 724,893; 
724,894; 759,613; 842,048; 


595 


506 DIGEST OF PATENTS 


987,417; 1,009,745; 1,014,982; 
1,014,983; 1,024,308; 1,025,983; 
1,025,984; 1,028,306; 1,067,881; 
1,099,676; 1,126,656; 1,235,253} 
1,282,356. 

XIV. 601,063. 

XV. 681,689; 722,630; 773,346; 
785,675; 892,455; 896,916; 
1,100,877; 1,129,575; 1,140,745; 

1,346,153; 1,440,833. 
2-Amino 

VI. 999,713; 1,027,132. 

3.3/-dicarbo . 
VI. 524,220. 
2.2’-Dichlor 
VI. 594,123; 888,522; 1,001,286; 
_ 1,094,448. 
3.3’-Dichlor 
VI. 988,000. 
Dichlor diacet 

VIO) 625.974. 

2.2'!-Dichlor 5.5/-dinitro 

VI. 982,509. 

Diethyl amino azo 
XIX. 551,885. 
Dimethyl diisopropyl 
XXIT. 1,314,924. 


2.2!-Dioxy 
VIG ESTO, 751. 
disulfo 


VI. 545,333; 578,580. 
XIV. 386,709. 
2.2/-disulfo 
VI. 791,524; 791,525; 791,526; 
1,041,919; 1,075,134. 
3-3'-disulfo 
VI. 1,012,960. 


Ethoxy 
VI. 496,392. 
Nitro 
VI. 1,009,952. 
2-Nitro 
493,583. 
2-sulfo 
VI. 995,160. 
sulfone 
484,521. 


sulfone disulfo 
VI. 432,989; 499,216. 
XIV. 386,709. 
2.5.2’.5/-Tetrachlor 
VI. 1,091,148. 
Benzimidazole: 
4-Amino N-salicylic acid 
Wie er. 127,201- 
Nitro a-methyl 
XV. 796,514. 
Benzo nitrile: 
XXII. tee 
Benzoie acid: 
III. 618,000. 
XVIII. 307,401; 316,471; 501,104. 
XXII. 702,171; 1,365,956; 1,458,491; 
1,463,190; 1,463,255. 
XXIV. (im)! 821,291; 1,207,952. 
eos ester 
XXIV. (m) 854,452. 
Tribrom tertiary butyl ester 
XXII. 1,397,913. 
Aldehyde 
XXII. 607,056. 
Alkoxy amino 
XXIV. (m) 1,317,250. 
Amino 
VI. 498,982. 


VI. 207,852; 878,964. 
VII. 848,354. 


297,852; 491,422; 583,635; 
585,104; 935,017; 964,786; 
1,338,506. 

XIV. 951,047. 


VI... 207,852; 
XLVS cost, 047% 
XXII. 748,101. 
4-Amino, amino alkyl esters 
XXII. 1,396,913. 
4-Amino, N-butyl esters 
XXIV. (m) 1,440,652. 
4-Amino, ethyl ester 
XXIV. (m) 748,101; 1,418,900. 
b-Chlor, ethyl ester 
XAT... 13393, 70"- 
2-Amino, 4-sulfo 
XII. 731,670. 
y-Brom propyl 4-nitro, ester - 
XXIV. (m) 1,476,934. 
2-Chlor 
VII. 669,794. 
2-Chlor 5-amino 
VI. 1,157,169. 
4-Chlor 2-amino 
III. 1,023,847. 
b-Chior ethyl 4-amino, ethyl ester 
XXIV. (m) 1,334,642. 
Dialkyl amino oxy benzoyl 
XIX. 675,215. 
3.4-Diamino, alkyl esters 
XXII. 761,998. 
Diethyl amino 
XVIII. 353,266. 
Diethyl amino 3-oxy 
XIX. 1,054,247; 1,106,185. 
Diethyl amino oxy benzoyl 
XIX. 694,149. 
Dimethyl amino oxy benzoyl 
XIX. 576,222; 576,223; 578,5783 
206, 3333 643,371. . 
Dimethyl amino 3-oxy benzoyl 
XIX. 1,002,825; 1,055,885. 
Dinitro 2-chlor 
XV. 667,689. 
Ethyl 4-amino 
VI. 967,615, 
Formyl 3.5-diamino 
VI. 1,001,183. 


Nitro 
XXII. 1,458,715. 
2-Nitro 
XALL, (650,332 
4-Nitro 


XXIV. (m) 950,936; 1,440,652. 
as-Nitro amino 
* VI. 344,075. 
4-Nitro 2-amino 
Vie 3310-73648 
5-Nitro 2-amino 
XXII. 720,876. 
4-Nitro 3-oxy 
XXIV. (m)- 610,348. 


Oxy 
XXL 024.7 nec 
4-Oxy 
XXIT. 407,906. 
4-Oxy 3-amino 
XXIV. (m) 625,158. 
o-Oxy ethyl 4-amino, ethyl ester 
(m) 1,334,641. 
1’-Oxy 2/-naphthoyl 
XIX. 3,194,380. 


per acid 

XXTV.i' (Gm) S21, 201 
2-sulfamin 

XXIV. (m) 604,503. 
sulfinid : 

XXIV. (m) 343,803. 
residues 


XXIV. (pl) 1,236,917. 


Benzophenone: 


XVIII. 290,891. 


VI. 1,028,493. 
4-Chlor dimethyl 4’-amino 
XVIII. 1,217,238. 
Diamino : 


“ee 5: 


VIS 447,180. 


INTERMEDIATE INDEX 


4.4’-Dichlor, brom phenanthrone quinone 


III. 1,016,604. 
3.3’-Dinitro 4.4'-diamino 
. 1,166,808. 
Tetraethyl diamino 
XVIII. 290,893; 297,413; 
353,264; 353,265. 
Tetramethyl diamino 
XVIII. 290,892; 297,414; 
308,748; 346,022; 
501,434; 603,016; 
680,732; 684,457; 


Benzoquinone: 


297,416; 


297,415; 
478,005; 
658,5043 
688,966. 


2-Nitro, formanilid 


XXIV. (m) 428,286. 
3-Nitro 6-oxy, chloride 
XXIV. (p) 729,024. 
Oxy, alcohol 

XXII. 1,023,758. 

2 and 4-Oxy, alcohol 
XXII. 526,786. 


360,792; 515,100. 


597 


salicylate (See Salicylic acid, benzyl ester) 
Trimethyl hexahydro oxy, anilin 


ITE. 1,09553203 1,209,163. 
2.6-Dichlor 
Li 2,025,147. 


3.6-Dichlor 1.4-dianilino 
II. 1,209,212. 

2-Oxy 5-methyl 1.4- 
III. 1,419,502. 


Benzo trichloride: 


Diis. 2,005,731. 
XVIII. 222,257. 
XIX. . 449,520. 


Benzoyl: 


acetic acid 2-carbo 
VI. 1,221,849; 1,234,894. 
acetyl peroxide 
(m) 717,016. 


chloride 
III. 935,590; 935,781; 938,618; 
938,619; 957,039; 957,040; 
957,041; 957,042; 957,146; 
989,602; 1,008,908; 1,022,781; 
1,023,248; 1,034,896. 
VI. 936,951. 
VII. 994,988; 997,766; 1,074,850. 
XVIII. 266,912. 
XXIV. (m) 512,590; 1,358,750; 
1,358,751; 1,388,573; 1,399,312. 
chloride, 3-Nitro 
. 1,078,504. 
XXII. 1,451,357. 
chloride, 2-, 3- or 4-Nitro 
Wile 7,012,853. 
chloride, 4-Nitro 
XXIV. (m) 812,554; 1,308,071; 1,360,994. 
XXII. 1,463,255. 
Di-, peroxide 
XXIV. (m) 717,016. 


4-Nitro, chloride 

XXIV. (m) 1,474,567. 
4-Nitro, ethanol 

XXIV. (m) 812,554. 
4-Nitro, diethyl amino ethanol 


Benzyl: 


XXIV. (m) 812,554. 
alcohol 
XXIV. (m) _1,313,6573 1,439,605. 
4-Amino, diethylamin 
VI. 610,345. 
4-Amino, sulfo 
VI. 1,041,146. 
chloride 
III. 656,668; 656,669; 1,329,435. 
VII. 259,629. 
Mm LVe. -3905s115- 
XVIII. 331,964; 331,965; 676,5553 
1,026,089. 
XXII. 1,306,221; 1,384,637; 1,463,190. 
XXIV. (m) 1,378,343. 
Dinitro, sulfo 
RV. 718,342. 
Hydro amin 
XXIV. (f) 714,931. 
5-Nitro 2-amino, sulfo 
VI. 1,001,458. 
Nitro, anilin 
XXII. 636,043. 


2-Nitro, anilin (See Anilin, 2-Nitro benzyl) 


4-Nitro, chloride 


33 


XXII. 691,157. 
Benzylidin: 

acetone 

VII. 262,695; 276,888. 

2-Amino, anilin sulfo 

XXII. 640,564. 

2-Nitro, acetone 

VII. 262,695. 

2 and 4-Nitro, anilin sulfo 

XXII. 622,854. 

4-Nitro, chloride 

XVIII. 283,766. 

XXII. 278,926. 
1.3-Butadiene: 

XXIV. (pl) 1,294,662; 1,415,468. 
Butene: 

XXII. 1,395,620. 
Butyl: 

alcohol 

XXIT. 1,451,357. 

XXIV. (m) 1,440,652. 

alkyl amin, N- 

XXIV. (m) 1,476,934. 

bromide, N- 

XXIV. (m) 1,331,712. 

chloral hydrate 

XXIV. (m) 768,398. 
Caffein, Hydroxy: (See Uric acid, 1.3.7- 

Trimethyl) 
Camphene: 

XXIV. (pl) 1,420,399. 
Camphorie acid: 

XXIV. (m) 674,686; 674,687; 686,998; 


86,999. 
Carbamie chloride: 


XXIV. (m) 1,427,506. 
Carbamid: 
XXIV. (pl) 1,355,834. 
as-Carbamids: 
XXII. 1,351,888. 
Carbazole: 
AIT. 1,196,1273.15324,717- 
VI. 401,634. 
VII. 1,051,856. 
XV. 919,5725 931,598; 956,348; 
1,128,371; 1,465,853- 
XXII. 685,895; 1,301,796; 1,318,212; 
1,348,722. 


N-acetic acid 

XV. 1,247,475. 
Diacetyl diamino 

XOVou et, 000,077. 
Diamino 

. 401,364; 632,503. 

Dimethyl diamino 

VI. 625,198. 
N-Ethyl 

III. 1,055,287. 

XV. 966,092. 
phenanthrene 
XXII. 1,303,639. 
sulfo acids 
XXII. 1,128,369. 
Tetramino 

VI. 1,107,764. 

Carbohydrate: 
XXIV. (t) 1,421,701. 
Carbon: 

bisulfide 

XV. 695,5333 773.3463 
tetrachloride 

III. 1,062,988. 
XXII. 1,474,928. 


1,081,599. 


508 


Carboxylation: 


XXII. 1,423,980. 
Carvacrol: 
XXII. 1,449,121. 
Casein: 
XXIV. (m) 601,072. 
Cellulose: 
XXIII. 650,715; 654,988; 679,203; 
679,204; 734,123; 854,374; 
1,366,023; 1,415,023. 
XXIV. (pl) 900,744; (t) 1,412,949. 
acetate 
MALIE, 9,425,364: 
XXIV. (pl) 1,368,867. 
Nitro 
XV. 622,299. 
XXIV. (pl) 1,368,867. 
plastic 
XXIV. (pl) 900,744. 


Chlor-acetie acid: (See Acetic acid, Chlor) 
Chlor anilin: (See Anilin, 2 or 4- ‘Chlor) 
Chloral: 
XVIII. 701,427. 
hydrate 
VII. 647,279. 
XIX. 625,641. 
Chloranil: 
III. 1,018,433; 1,065,063; 
1,431,656. 
XV. 820,501; 1,128,368; 1,405,446; 
1,452,805. 
Chlorbenzene: (See Benzene, Chlor) 
Chlorhydrin: 
XXII. 1,295,339; 
1,386,118; 
1,394,664. 
a-Chliorhydrin: 
VI. 440,953. 
XXIV. (m) 1,230,185. 
Chlorpicrin: 
XVIII. 1,402,195. 
Chromotropie acid: 
VI. 718,181. 
Chrysazin: 
IIT. 595,350. 
4.5-Diamino 
III. 605,921. 
4.5-Diamino, disulfo 
III. 656,669; 658,513. 


1,196,422; 


1,315,229; 
1,393,191; 


1,308,796; 
1,388,016; 


4.5-Dinitro 

III. 623,219. 

Chrysoidin: 

VI. 602,639; 602,641. 
Amino 

VI. 586,865. 
4-Amino 

VI. 936,456. 


Cinchonie acid: 
Methoxy phenyl 


XXIV. (m) 1,076,160. 

Phenyl 

MXDV2 | Cm) 14361, 126- 
Cinnamie acid: 

VII. 233,458. 
XXIV. (m) 625,159. 
2-Amino 

VI. 297,852. 
4-Amino 

VI. 297,852. 
4-Amino, methyl ester, 

VI. 249,926. 


a-Acidyl amino, esters, 
XXIV. (m) 1,437,802. 
2-Nitro 
VII. 233,458; 233,459; 233,460. 
2-Nitro dibrom hydro 
VII. 233,458. 
Citrie acid: 
XXIV. 
Cleve’s acid: 
Coumarone: 
OX L Veep) 
Creosote ethers: 
XXIV. (m) 501,235. 


(m) 602,10 
(See Ie Naphthol 5-sulfo) 


1,263,813; 1,360,665. 


DIGEST OF PATENTS 


Cresidin: 
VI. 602,640; 933,446; 935,018; 
978,580; 999,558; 999,944; 


1,001,183; 1,024,031; 1,052,135; 
1,074,946; 1,079,415; 1,087,427; 
1,169,329; 1,241,153. 
Cresol: 
o| 221, i7 per eco lease 
XV. 603,755; 629,221; 1,265,836; 


1,265,837. 


XXIT. 1,409,588; 1,439,128; 1,445,668. 
XXIV. (e) 1,292,266; (m) 1,028,074; 
(pl) 1,414,139. 
2-Cresol: 
VI. 386,192. 
3-Cresol: oe 


III. 1,028,074. 


XXII. 798,807; 1,425,392; 1,425,393. 


XXIV. (pl) 1,088,677; 1,088,678; 
(m) 1,412,937. 
3 and 4-Cresol: 
XXII. 655,117; 656,263; 1,364,547. 
4-Cresol: 


VI. 718,389; 737,445; 987,799. 
XXIV. ém) 966,820; (pl) 1,088,678; 
1,306,681. 
Cresol, a-Asine! 
XV. 671,908. 
4-Cresol: 
2-Amino 
VI. 536,532; 536,878; 536,879; 
536,880; 557,438; 617,963; 
826,282. 
3-Amino 
VI. 993,549. 
VII. 867,305. 
XIX. 578,578; 643,371; 695,441; 
738,227. 
2-Cresol, 4-Amino: 
XIV. 636,065. 
4-Cresol: 
2-Amino, 6-sulfo 
VI. 1,025,267. 
3-Amino, 5-sulfo 


VI. 739,069. 
2-Cresol, 5-Amino: 

VI. 987,362. 

XV. 660,067. 


4-Cresol, 2-Amino, methyl ester: 
VI. 1,371,979; 1,378,388. 
3-Cresol, 2-Amino dinitro: 


VI. 935,031. 
4-Cresol, 2-Amino ethyl: 
VI. 897,529. 


2-Cresol, 6-Amino 4-nitro: 
VI. 924,231. 
Cresol, 4-Amino, sulfo: 


VI. 396,293. 
2-Cresol, 5-Amino, 4-sulfo: 
VI. 722,716. 

3-Cresol: 


carbo (See 3-Cresotinic acid) 


XXIV. (t) 1,344,951. 
4-Chlor 
XXIV. (m) 1,036,087. 
4-Cresol, 3-Chlor: 
XXII. 785,003. 
2-Cresol, 6-Chlor 4-amino: 
XV. 775,570. 
XXII. 775,570. 
Cresol: 
Dinitro 
XV. 596,559. 
Ethyl amino 
XIX. 516,585; 1,006,738. 
3-Cresol, 6-Isopropyl: 
XXIV. (m) 1,332,680. 
4-Cresol, 3-Nitro: . 
XXII. 1,304;150; 
2-Cresol, Nitroso: 
; XV. 901,970. 


4-Cresol: 
5-Nitro 2-amino 


‘ 


sf 


INTERMEDIATE INDEX 


VI. 676,494; 676,495. 

6-Nitro 2-amino 

VI. 887,348. 

pera acid esters 
1,425,392; 1,42 ; 
Cresol, 4-Thio: ca 

III. 1,018,836; 1,062,990. 
Cresotinic acid : 

394,841; 395,634; 396,294; 
1,474,587. 
2-Cresotinie acid: 

VI. 484,521; 980,251; 980,521; 
1,021,364; 1,021,365; 1,021,366; 
877,052; 877,054; 887,620; 
947,876; 950,359; 995,494; 
998,139; 999,028; 1,004,609; 
1,004,610; 1,026,089; 1,042,493; 
1,044,836; 1,219,166; 1,244,149. 
2 or 4-Cresotinie acid: 

VI. 943,536. 

XXIV. (m) 749,634. 
3-Cresotinie aci 

VA 787,046. 

- 1,065,405. 
XXIV. (t) 1,344,951. 
4-Cresotinie acid: 
XVIII. 1,065,405. 
XXII. cate 978,802. 
2-Cresotinie acid, 4-Amino: 
XIV. 6 36,065. 
2.6-Cresotinic acid, 4’-Amino benzoyl 4- 
amino: 

VI. 1,098,388. 

Cresotinie acid, Methylene 2.2/-di-: 


XVIII. 


XVIII. 976,417; 978,799; 978,800; 
978, oie 978,802; 1,023,977; 
1,034,1 


3-Cresotinie acid, Reiswethyl acetyl: 


XXIV. (m) 1,338, 207. 
Cresylemne diamin: 
XV. 561,277. 
Cresylie acid: 
XXII. 1,445,668. 
Croton aldehyde: 
XXII. 1,445,544. 
Crotonie acid: 
XXII. 1,445,544. 
Cumoarin: 
XXIV. (pl) 1,294,836. 
ps-Cumene: 
XVIII. 1,470,554; 1,470,555. 
Cumidin: 
XIV. 613,911. 


ps-Cumidin: 
VIL. 877,743. 


sulfo 
XIV. 386,709. 
Cyanhydrins, Alkylene: 
XXII. 1,388,076. 


Cyanimid, Disodium: 
VII. 860,900. 
Cyananthrene: 
III. 837,775. 
Cyanuric chloride: 
III. 1,437,783. 


XXIV. (e) 1,390,378. 
4-Cymene: 
XXII. 1,333,694. 
XXIV. (m) 1,332,680. 
Cymene: 
Amino 
XV. 1,314,929. 
XXIV. (m) 1,306,512. 


2 or 3-Amino 
VI. 1,314,921; 
Acetyl amino 


1,314,922. 


XXIV. (m) 1,306,512. 
Nitro 
SN Met 254.029. 
XXII. 1,314,920. 
XXIV. (m)_ 1,332,680. 


4-Nitro acetyl amino 
XXIV. (m) 1,306,512. 
sulfo 


509 
DQG Sahay 
Sy 
<XIV. (m) 1,432,298. 
Cymidin sulfo: ana 
XXIV. (m) 1,432,298. 
Cymol: 


ON eet SILO Sle 
Hydrazin of 2-amino, 6-sulfo 
VI. 1,447,485. 
Cymyl hydrazin 3 or s5-sulfo: 
XXIV. (m) 1,432,208. 
Dehydrothiotoluidin: (See Toluidin, 
Dehydro thio.) 
Dialdehyde, Chlor: 


XVIII. 1,219,166. 
Diamin Black Blue E: 
- 517,533- ; 
oer naphthols (See Amino naphthol, 
1- 
Dianilin: 
VI. 541,750. 
Dianisidin: 
VE. 357.273; 287:2743. 417,294, 
447,302; 467,162; 476,371; 
481,034; 493,563; 498,874; 


509,929; 512,493; 516,757; 
516,760; §21,986; 524,069; 
524,070; 525,492; 532,125; 
542,073; 558,344; 558,613; 
560,449; 561,694; 563,386; 
569,392; 583,635; 584,981; 
588,181; 602,540; 611,597; 
620,368; 666,866; 682,510; 
728,477; 842,548; 860,221; 
888,036; 916,323; 1,042,356; 
1,082,923; 1,157,525; 1,160,406; 
1,282,356. 
2.2’-Dichlor 
VI. 964,918; 964,920. 
Dianthranilie acid: 
VII. 623,294. 
1.2/-Dianthraquinonyl amin: 
III. 860,480. 
1.1’-Dianthraquinonyl: 
amin, 4.4/-Diamino 
III. 893,508. 
2.2/-dialdehyde 
III. 1,004,433. 
Dibenzoyl 5.5’-diamino, thio ether 
III. 1,059,607. 
4.4/-Dichlor 2.2’-dimethyl 
III. 1,058,604. 
6.6’-Dichlor 2.2/-dimethyl 
III. 929,442. 
2.2'-Dimethyl 
III. 876,810; 955,105; 1,077,115. 
imid 
III. 1,052,480. 
w-Tetrachlor 2.2’- dimethyl 
TIL,” 2,847,513. 
1.1/-Dianthrimid: 
III. 960,182. 
1.1/-Dianthrimin. 
III. 996,109. 
Dianthrone: 
III. 999,680. 
Diaryl ethers: 
XXII. 1,099,761. 
ketone, 4.4’-Diamino 
VI. 1,472,334. 
Diazotization: 
XU eat o 20.4435 
Dibenzanthrone: 


Dibenzoyl 4.4’-diamino: 


III. 1,093,427; 1,201,968; 1,207,762; 
1,464,079. 
Amino 
III. 1,128,836; 1,202,260. 
Iso- 
III. 1,063,000. 
Nitro 


TII. 1,169,404; 1,204,639. 
Dibenzidin methane: 
VI. 516,468. 


510 


Dibenzyl: 
4.4'-Diamino, 3.3’-disulfo 
VI. 619,518. 
4.4’-Dinitro, 2.2’-disulfo 
XIV. 613,911. 
Dibutyl: 
amin 
XXIV. (m) 1,358,750; 1,358,751. 
amino ethyl alcohol 


XXIV. (m) 1,358,750; 1,358,751. 
Diethyl amin: 
XIX. 613,926,; 615,791. 
XXII. 1,403,117. 
XXIV. (m) 619,549; 624,772; 625,159; 
812,554; 1,316,047; 1,334,642; 
1,403,117. 
Chlor ethyl 
XXIV. (m) 1,414,333; 1,429,922. 


Diethylanilin: (See Anilin, Diethyl.) 
Diethyl sulfate: 
XXII. 1,427,215. 
b-Diketones, aliphatic 
XII. 658,593. 
Dimethyl amin: 
VI. 515,100. 


XXIV. (m) 543,214. 
4-Amino benzyl 
» 999,713. af } 
Dimethylanilin: (See Anilin, Dimethyl.) 
Dimethyl: 
sulfate 


III. 727,389. 
XIX. 656,426. 
1.1’-Dinaphthyl: 
2.2/-Dimethoxy 
XXII. 1,454,205. 
4.4’-Dioxy 3.3’-dicarbo, ketone 
XXII. 1,453,659. 
Dinaphthylene thiophene: 
1,471,150. 
2.2’ Dinaphthyl sulfone: 
XXIV. (t) 1,375,976. 
1.2’Dinaphthyl _ urea, 
disulfo: 
VI. 675,632. 
2.2/-Dinaphthyl urea: 
5.5’-Dioxy 7.7/-disulfo 
VI. 662,122; 1,015,375; 
1,058,692; 1,282,356. 
5.8’-Dioxy 7.6/-disulfo 
VI. 675,629. 
1-Dinaphthylamin: 
Vio 251,677. 
XVIII. 680,732. 
2-Dinaphthylamin, 5-s’-Dioxy 7-7/-disulfo: 
VI. 656,620; 656,621; 1,009,796; 
1,009,797; 1,012,960; 1,020,670; 
1,022,287; 1,022,288; 1,038,209; 
1,038,210; 1,052,136; 1,058,562; - 
1,078,926; 1,082,923; 1,457,235- 
2.2/-Dinaphthylamin, 
disulfo urea: 

VI. 663,498; 1,087,429; 1,087,430; 
1,088,735; 1,090,379. 
Dinaphthyl, 4.4/-Dioxy 3.3’dicarbo, ketone: 

VI. 1,453,660. 
as-Dinitranilin: 
VI. 381,045; 381,046. 
2.4-Dinitranilin: 
VI. 525,656; 912,138; 982,953; 
980,000; 989,001. 
XV. 626,897. 
2.6-Dinitranilin: 
VI. 932,28¢ 
2.4-Dinitranilin 6-sulfo: 
VI. 978,865. 
Dinitrobenzene: 
and derivs.) 
Dioxindole: 
VII. 943,678. 
Diphenetidin: 
VI. 342,432; 380,067; 388,185; 
415,258. 


5-5/-Dioxy 7.7/- 


1,052,137; 


(See Benzene, Dinitro 


5-5’-Dioxy  7.7/- 


DIGEST OF PATENTS 


Diphenetol, Dinitro: 
VI. 306,960. 
Diphenie acid, Amino: 
VI. 297,852. 
Diphenyl: 
XXII. 1,322,983. 
4.4’-Diphenyl: 
III. 993,736. 
Diphenyl: 
4-Amino 4’-chlor 
III. 1,090,636. 
3-Amino 4-methyl, 
1,045,196. 


sulfone 


VI. 380,402. 
4.4’-Diamino, 3.3’-dicarbo 


14870855: 
Diphenyl urea: 
Diamino 
VI. 946,051; 946,052; 1,012,853. 


3.3/-Diamino 
VI. 678,323; 946,050; 997,061; 
1,025,983; 1,025,984; 1,078,504; 
1,082,581. 
4.4'- Diamino 
VI. 1,126,466; 1,173,077. 
4.4!- Diamino, 3-3 '.disulfo 
687,171; 1,009,740; 1,009,741; 
1,019,321; 1,049,100. 
4.4!- Diamino dibenzoyl diamino, disulfo 
VI. 1,082,925. 
4’ altt -Diamino 


dibenzoyl 4.4'-diamino, 


Diphenyl: 
4.4'-Diamino, ketone 
VI. 1,472,333. 
4.4’-Dichlor, sulfone 
III. 993,735. 
Ethenyl 4-dialloxy, amidin 
XXIV. (m) 1,384,637. 
Methylene, diimin 
XXIV. (pl) 1,418,772; 
Diphenylamin: 
VI. 211,671; 297,852; 468,049. 
ee Az0ra ase 
XV. 610,541; 658,055; 727,387; 
728,623; 1,471,854. 


1,429,267. 


XVIII. 248,153; 252,203; 816,457. 
XXII. 1,308,356; 1,314,538; 1,392,942; 
1,422,494. 
4-Alkyl 4'-oxy 
xX 1,099,039. 
4-Amino 


II. 796,715. 
VI. 517,533; 983,805; 1,056,493. 
AV... 722.364. 
4’-Amino benzoyl 
Visi rr Gre: 
4’-Amino 2.4-dinitro 
XV. 764,733. 
4-Amino 3-methyl 4’-oxy 
XV. 747,643. 
4-Amino 3-methyl 4’-oxy 3 '.chlor 


742,189. 
4-Amino 2-nitro 4/-oxy 
XV. 740,465. 


4’-Amino 4-oxy 
XV. 660,770; 710,766; 723,154. 
4-Amino, 2-sulfo 
VI. 605,103. 
IX. 1,059,571. 
4-Amino, 4/- sulfo 
XXII. 860, 073. 
4-Amino tolyl 4'-oxy 
XV. 700,151. 
2 or 4- Anilino 2'.4/-diamino, 3-sulfo 
IX. 1,162,109. 
sat oxy diamino, m-sulfo 


1,162,109. es 
Benzyl 
XVIII. 346,022; 353,265. 
2-carbo " 


INTERMEDIATE INDEX 


XV. 1,081,638. 
Dialkyl 4-amino 4’-oxy 

XV. 693,633. 
Diamino 


VI. 525,245. 
i ta eae a 
- 671,543. 
XXII. 805,890. 
4.4’-Diamino, 2.2’-disulfo 
VI. 647,237. 
2.4-Diamino, 3’-sulfo 
807,289. 
4.4’-Diamino, 2-sulfo 
_ VI. 536,431; 594,996; 603,009. 
Dichlor nitro 
XV. 1,329,898. 
Dimethyl 4’-amino 2.4-dinitro 
; 653,670. 
Dimethyl 4-amino 4’-oxy 
XV. 693,632; 698,555; 960,919. 
Dimethyl 4’-amino 4-oxy 3-chlor 
XV. 776,264. 
Dinitro 
XXII. 1,309,580. 
2.4-Dinitro 
XXIV. (e) 1,326,947. 
2.4-Dinitro 5-amino 4’-oxy 
XV. 650,327. 
2.4-Dinitro 2'.3’-carbo 
XV. 628,608. 
2.4-Dinitro 5’-chlor 2-oxy 
XV. 651,077. 
2.4-Dinitro 5-chlor 4’-oxy 
- 650,327. 
XXII. 650,327. 
2’.4’-Dinitro 5-chlor 4-oxy 3-methyl 
7751570. 
2.4-Dinitro 4/-oxy 
V. 635,168; 635,169; 642,256; 
647,846; 647,847; 660,058; 
665,726; 688,999. 
2.2’-Dinitro, 4.4’-disulfo 
IX. 743,778. 
2.6-Dinitro, 3.4-disulfo 
VI. 879,053. 
XVIII. 886,815. 
2’.4’-Dinitro, 5-sulfo 
XV. 644,959. 
2.4-Dinitro 5-thiocyan 4’-oxy 


feat 7355775. 
4.4’-Dioxy 
XV. 736,380. 


2.4'-Dioxy 4-amino 
4'’.4’'-Dioxy diphenyl 4.4’-diamino 
are haa 657,769. 
- 763,193. 
Ethyl 
VI. 297,852. 
Ethyl _4-amino 3-methyl 
732,090. 
sym-Hexanitro 
XV. 690,271. 


Methyl 
VL. 297,852. 


VIET, 248,153; 266,912; 327,953: 
333,861; 353,264; 353,266. 
4-Methyl 3-amino 4/-nitro, 2-sulfo 
II. 800,735. 
2 or 4-Naphthoxy 2’.4’-diamino, 3-sulfo 
1,162,109. 
2 or 4-Naphthylamin 2/.4’-diamino, 3-sulfo 
I 1,162,109. 
2-Nitro, 4-sulfo 
XV. 628,607. 
4-Nitro 2-amino 4/-oxy 
XV. 695,533. 
4-Nitro chlor 2-sulfo 
V. 641,100. 
641,100. 


4’-oxy 3/-chlor 


VI. 767,069; 767,070; 839,489. 
413,048; 413,050. 


511 
XV. 1,006,715. 
Oxy dinitro 
AV. 625,719. 
4-Oxy dinitro 
XV. 706,969. 
2/-Oxy 2.4-dinitro 
XV. 639,606. 
4’-Oxy 2.4-dinitro 
XV. 692,174. 
4-Oxy dinitro, 2-carbo 
667,689. 
4-Oxy 4’-methoxy thio 
- 1,098,260. 
4-Oxy 4/-methyl 
1,098,259. 
4-Oxy 3-nitro s-sulfo 2’.4/-dinitro 
650,292. 


Phenyl 4-amino 4’-oxy 
XV. 790,167; 1,302,671. 

2 or 4-Phenoxy 2’.4/-diamino, 3-sulfo 
IX. 1,162,109. 
III. 538,2rs. 

Thi 


io 
XXIT. 282,835; 286,526. 
4-Tolyl 4-amino 4/-oxy, sulfo 
XV. 864,644. 
Diphenylene oxide, Diamino: 
VI. 423,569. 
Diphenyl ether: 
3-Amino 
VI. 958,830. 
2-Amino 4-chlor 
VI. 950,405; 953,033; 953,034; 
958,830. 
2-Amino sulfo 
VI. 1,166,346. 
2-Amino 4-sulfo 
VI. 1,042,198. 
835,882. 
4-Amino 2-sulfo 
VI. 1,042,198. 
2.4-Diamino 4’-carbo 
VI. 981,276. 
2.4-Diamino 4’-sulfo 
VI. 879,552. 
Diphenyl: 
3-Amino 4-methyl 2/-carbo, ketone 
III. 1,035,023; 1,067,046. 


VI. 447,189. 
Diphenyl methane: 
Vi. 515,897. 


VI. 1,472,333. 
XVIII. 471,638. 
3-3’-Diamino 4.4’-dimethyl 
1,233,742. 
4.4’-Dichlor 
III, 1,037,410. 
Dinitro dioxy 
960,652. 
4-Phenoxy 2’.4”-diamino, 3-sulfo 
1,162,109. 
Diphenyl sulfone, 2-Amino 4-acetyl amino 
4/-methyl 5/-sulfo: 
VI. 1,467,711. 
Diphenylimid, Carbo: 
XVII. 647,281. 
3.6-Diphthaloylie acid, N-Ethyl carbazole: 
TIE 4,055,207 
Dipropyl amin: 
XALV. 7 Gm) 1,403,127. 
Distilbene: 
Azo azoxy, 2.2/-disulfo 
XIV. 951,046; 951,047; 951,048; 
951,049. 
4.4’-Diamino azo, tetra o-sulfo 
XIV. 360,553. 
Ditolyl amin, 4.4/-diamino: 
VI. 575,904. 
Ditolidin methane: 
Amino 


512 


VI. 531,149. 
Tetra amino 
Vives 4gyete. 
2.2/-Ditolyl methane, Diamino: 
XVIII. _ 473,453. eae 
4.4’-Ditolyl methane, 3.3’-Diamino: 
Wiener. 342.83 4. 
3.3/-Ditolyl methane: 
4.4’-Dihydrazin 
VI. 1,166,346. 
4.4’-Dipyrazolone 
VI. 1,166,346. 
Ditolyl urea, 3.3’-Diamino: 
VI. 1,078,503. 
Dusatogen: 
VII. 251,500. 
Eegonin: 
Anhydro 
XXIV. (m) 1,352,082. 
Dihydro anhydro 
XXIV. (m) 1,352,082. 
Epichlorhydrin: 
III. 958,850; 1,045,805. 
Ethane: 
sym-Dibrom 
XXIV. (m) 1,308,413. 
Nitro 
XXIV. 
Ethanol: 
Diethyl amino 
MXIV: §Gn) 2,377,2503 1,317:251. 
Nitro benzoyl diethyl amino 
XXIV. (m) 812,554. 
Ethionie acid: 
XVIII. 262,680. 
Ethyl acetate: (See Acetic acid, ethyl ester.) 
Chlor (See Acetic acid, Chlor ethyl ester.) 


(m) 1,356,877. 


Ethyl: 
alcohol 
XXIV. (m) 1,045,378; 1,045,379; 

1,045,759. 

Urethane of trichlor 
XXII. 1,311,824. 
XXIV. (m) 1,427,506. 
amin 
XIX. 649,716. 
amin, 4-Methoxy phenyl 
XXII. 1,016,092. 
bromide 


VI. 454,840; 880,293. 
VII. 662,755. 
43,0606. 
XML V 8 Gri) 9550053 Fz. 
chlor carbonate 
III. 958,325. 
XXIV. (m) 570,416. 
chloride 
Vi 472,121> 6044,402. 
XIX. 499,927. 
Dioxy di-, sulfide 


XXIV. (m) 1,422,869. 
iodide 
TIT. — 7,128,836. 
XVIII. 204,798. 
XXIV. (m) 464,861. 
Ethylene; 
chlorhydrin 
XXIV. (m) 1,358,750; 1,358,751. 


diamin diacetacetic ester. 


XXII. 361,690. 
Dichlor 
VII. 943,560. 
XXII. 1,430,324. 
Dichlor ethoxy 
VII. 804,149. 
XXII. 804,148. 
oxid 


III. 1,014,204. 
XXIV. (m) 1,418,900. 
‘Trichlor 

VII. 943,561; 1,467,598. 
Trihalogen 

VII. 910,839. 


DIGEST OF PATENTS 


Ethylidene diacetate: 
XXII. 1,440,918. 
Flavopurpurin, Amino: 
III. 450,037. 
Fluorane, Dichlor dimethyl: 


XXII. 785,003. 
Fluorene: 
XXII. 1,374,605. 


Fluorenone, 3.6-Dibrom: 
Ii 91,216,027. 
Fluorescein: 
chloride 
XIX. 
Dibrom 


493,241; 615,791. 
617,627. 


649,716. 
Formaldehyde: 
III. 658,513; 658,514; 704,798; 
738,614; 765,576; 785,121; 
785,122; 785,123; 790,079; 
791,869; 868,399; 871,507. 
VI. 515,897; 516,468; 516,756; 
516,757; 516,758; 516,759; 
516,760; 519,522; 519,523; 
541,859; 542,073; 1,122,564; 
1,338,506; 1,362,936. 
VII. 662,754; 662,755. 
IX. 763,756; 932,266; 955,080. 
XV. 722,630; 801,598; 960,652; 
T,1O5,S3.0¢ ; 
464,538; 538,215. 
445,684; 613,113; 625,536; 
643,371. 
666,579; 704,490; 715,748; 
875,415; 891,753; 910,648; 
1,437,483. 
(f£) 1,345,649; (m) 598,914; 
601,072; 811,884; 854,452; 
1,056,881; 1,299,214; 1,426,348; 
(p) 1,297,685; (pl) 1,088,677; 
1,088,678; 1,306,681; 1,310,087; 
1,310,088; 1,345,694; 1,355,834; 
1,368,867; 1,369,352; 1,374,526; 
1,397;1443 1,414,139; 1,429,265; 
(t) 1,336,759; 1,344,950; 
1,344,951; 1,344,952; 1,375,976; 
1,399,510; 1,421,701. 
Para 
XIX. 1,403,888. 
XXIV. (pl) 1,429,267. 
hydrosulfite 
XXII. 769,593; 804,157; 812,124; 
814,031; 814,032. 
sulfoxylate 
Ill. 1,204,639. 


XXII. 793,559; 841,999; 871,600; 
885,566; 885,567; 887,050; . 
935,815; 1,006,793. 

XXIV. (m) 1,053,300. 


Formalin: (See Formaldehyde.) 
Formanilid, 3-Amino: 
VI. 1,087,480. 
Formaurin, Dimethyl dicarbo, leuco prod- 
uct: 
XVIII. 976,417. 
Formie acid: 
III. 1,045,805. 
VI. 1,020,756. 


XXL. 14457062 

XXIV. (m) 428,286. 

Chlor, ethyl ester 

XXIV. (m) 1,375,949. 
Fuchsin: 

XVIII. 250,207. 
Furfural: 

XXII. 1,322,054; 1,357,467. 

XXIV. (pl) 1,398,146; 1,441,598. 
Fustie: 


VI. 409,384. 
Gallamie acid: 


XIX. 551,885. 
Gallamid: 
XVII. 898,842. 


INTERMEDIATE INDEX 


Gallie acid: 

ITI. 348,613; 617,981; 623,069. 

Gamma acid: (See 1-Naphthol, 7-Amino, 
3-sulfo.) 
Glycerin (Glycerol):, 

III. 786,085; 787,859; 790,079; 
793,558; 898,104; 809,892; 
809,893; 809,894; 811,471; 
818,336; 818,992; 820,379. 
VII. 661,871, 894,006. 

XV. 636,066; 645,738; 728,623; 

763,193; 880,936. 
XXIV. on 295,825; 466,708; 741,585; 
1,424,137. 
Glycocol: 2 ene! 
VII. 669,794; 680,395. 
Ph Vene (ii) 16a T7107. 
Ethyl phenyl 
VII. 617,651. 
Ethyl 2-tolyl 


Glycol: 
acetate 
XXII. 1,430,324. 
chlorhydrin or bromhydrin 


XIV. (m) 1,308,414. 
Dimeth 
XXIV. (£) 1,418,904. 
Dithio 
XXIV. (m) 1,422,869. 
Trimethylene 
XXIV. (m) 1,286,944. 


Glyecolie acid: 
anilid 2-carbo 
VII. 768,455. 
2-Chlor phenyl thio 
VII. 916,030. 
4-Chlor phenyl thio 
VII. : 899,152. 
Chlor tolyl thio 
VII. 902,029. 
Di-, guaiacol ester 
XXIV. (m) 948,084. 
6-Methoxy 4-chlor 3-methyl thio 
Wilewet.6025,135- 
Naphthalene 2.6-dithio 
VII. 1,444,277. 
2-Nitro phenyl thio 
959,617. 


VII. 848,354. 
Thio 2-carbo 
VII. 867,679. 
2.4-Xylyl thio 
VII. 881,624. 
Glycollid: 
VII. 768,455. 
Glyoxylie acid: 
III. 1,079,568. 
4-Amino phenyl 
XXII. 676,860. 
Methyl 4-amino phenyl 
XXII. 708,511. 
Guaiacol: 
XXIV. 
ester 
XXIV. 
Guanidin: 
XXII. 1,417,369. 
5.5’-Dioxy 7.7/-disulfo 2.2'-dinaphthyl 
V. 677,517. : 
5.5/5’'-Trioxy  7.7/7”-trisulfo, 
naphthyl 
Nia 67735 10. 
Gun eotton: (See Cellulose, Nitro.) 


(£) 1,345,649; 1,418,904. 
(m) 624,772. 


2.2'2”-tri- 


H. aeid: (See 8-Amino 1-Naphthol 3.6- 
disulfo.) 
Halogenation: 
XXII. 721,961; 1,308,763; 1,345,373; 
1,384,909; 1,420,346. 
Heliotropin: 
XXIV. (f) 804,682. 


913 


Hematoxylone, a-Anhydro tetra methyl: 
VE 17106,7515 
Hexamethylenetetramin: 


XXII. 852,993; 860,636. 
XXIV. (m) 567,068; 607,172; 690,804; 
852,993; 869,636; 1,076,160; 
(pl) 1,306,681; 1,375,959; 
1,435,801. 
Hydantoin, aq-Phenyl: 
VII. 714,000. 
Hydrazin: 
Alphyl 
XXIV. (m) 1,425,929. 
Aromatic 
XII. 324,630. 
XIV. 386,709. 


6-Biom 4-sulfo 2-tolyl 
XII. 1,109,919. 
2-Chlor aryl, sulfo 
XII. 1,098,600. 
2-Chlor phenyl, 3 or 5 sulfo 
XII. 982,050; 1,098,600. 
3-Chlor 2-tolyl, 5-sulfo 
I. 935,370. 
hydrate 
Liter 285;727 
Nitro phenyl 
XII. 627,690. 
4-Nitro phenyl 
XII. 627,690; 988,870. 
2-Oxy s5-sulfo 3-carbo phenyl 
N/T 2705325. 
Phenyl 
XVIII. 580,766; 609,598; 621,393. 
Phenyl, sulfo 
xX Tia 24,630: 
XIV. 386,709. 
Phenyl, 2 and 4 sulfo 


XII. 969,428; 972,951. 
sulfo 

XIV. 386,700. 
2-Tolyl 
XVIII. 664,450. 
4-Tolyl 
XXIV. (m) 503,066. 


Hydroquinone: 


XV. 594,106; 594,107. 
XOX Wie (pts 207,005- 

Acetyl 2.5-diamino . 
View 7395215. : 
4'.4”-Diamino, diphenyl diether 

VI. 839,360. 
Hydroxylamin: 
III. 1,216,134; 1,464,079. 
VI. 447,189 
VII. 647,279 
disulfo 
SOT Pare Ol st 777. 


Hydroxylation: 
XXII. 1,062,351; 1,297,7925 1,320,454; 
1,321,271; 1,430,184. 
Tehthyol sulfo acid: 
XXIV. 318,662; 495.124; ©71,135; 
709,321. 
Immedial Black V: 
XVS> Ga5.7172 
Indanthrene: 
III. 753,659; 785,121; 844,914; 
893,837. 
Blue 
III. 948,204; 970,378. 
4.4’-Diamino 3.3’/-dibrom 
III. 785,123. 
Dianthraquinonyl 
III. 1,0523480. 
3.3/-Dimethyl 
Tib922,567- 
Indene: 
XKIVS. Clee 263.8136 1,294,836; 
1,360,665. 
1.3-Diketo hydro 
VI. 1,075,305. 


514 _ DIGEST OF PATENTS 


Indigo: 

VII. 251,501; 720,217; 765,687; 
765,996; 856,776; 872,115; 
872,280; 883,703; 888,230; 
899,863; 920,156; 937,040; 
937,:041; 997,766; 1,012,363; 


1,043,682; 1,061,781; 1,070,541; 


1,074,850; 1,473,887. 
Dehydro 
VII. 1,012,363; 1,042,679. 
XXIII. (In) 1,448,251. 
4.4’-Diamino 
VII. 940,586. 
Dibrom 


VII. 916,031; 918,920; 1,043,468. 


5.5’-Dibrom 
VII. 1,414,335. 
6.6’-Diethoxy, thio 
VII. 963,813. 
5.5’-Dimethyl 
VII. pararaae 


b-Naphthy 
VII. 932,334. 
hio 


VII. 867,715; 898,738; 947,030; 
954,273; 955,659; 959,617. 
Trichlor 
VII. 915,338. 
white 
VII. 706,921; 812,598. 
Indirubin: 
VII. 876,158. 
Indogen: 
VII. 250,035. 
Indogenie acid: 
VII. 250,036; 259,260; 259,261. 
Indole: 
XII. 698,328. 
Dihydro methyl 
vps 913,513. 


VI. 719,048; 719,049; 791,525; 
791,526; 1,114,750. 
2-Methyl, sulfo 
VI. 978,439. 
2-Methyl, 6-sulfo 
AYA Ns oe th ge Poh 
Indophenol: 
XV. 665,547; 696,751; 708,662; 
736,403; 741,030; 778,478; 


1,209,580; 1,302,671; 1,471,854. 


Benzyl methyl 
XV. 1,449,681. 
2.6-Dichlor 
_ XV. 779,860. 


XV. 763,320. 


DEV. ag h2o;97 1. 
XXII. 1,128,370. 
thio. sulfo 
679,199. 


625,268; 646,841; 713,437; 
715,074; 737836; 778,725; 
876,158; 894,579; 898,452; 
904,867; 960,098. 
6-Amino thio 

VII. 1,081,898. 


Indoxyl : 
VII. 


II. 1,074,405. 
4-Chlor 5-brom 
VII. 957,683. 
Diacetyl 
VII. 626,231; 657,359; 699,581. 
Dibrom, thio 
VII. 1,108,057. 
4.5-Dichlor, carbo, ester 
VII. 955, 410. 
Dimethyl 4’-amino a-anilino, thio 
VII. 997,260. 
7-Methyl 
VII. 1,028,911. 


6-Nitro diacetyl 
VII. 1,266,092. 


VII. 819,348; 836,309; 848,356; 
850,827; 867,714; 875,649; 
954,273; 997,260. 
Indoxylie acid: 
VII. 690,332; 778,725. 
Isatin: 
III. 908,156. 
VII. 240,941; 240,942; 259,629; 
310,604; 625,268; 841,003; 
848,355; 867,714; 874,649; 
ph Ee 943,678; 
394; 968,697; 1,028,911. 
XXIV. coy 1,181,485; 1 aoa 


1,350,408. 
Acetyl 
VII. 923,959. 
a-anilid 


VII. 647,279; 647,280; 697,545; 
848,356; 850,444; 954,273; 
_. 99954393 1,025,174; 1,144,577. 
chloride 
VII. 1,122,790. 
5-Chlor, 4 "chlor a-anilid 
VIL. “1, x08,086575,1575455- 
Dibrom 
VII. 898,452; 958,464; 958,465; 
961,397; 961,399; 998,596; 
1,001,919. 
5.7-Dibrom 
VII. 1,051,856. 


VII. 980,140. 
5-7-Dichlor 

VII. 1,074,405; 1,266,092. 
XVIII. 1,434,983; 1,466, 687. 
5.6-Dichlor, a-anili 

rie ' 1,147,778. 


VII. 961,398. 
s-Methyl 4-toluidin 
VII. 310,604. 
Isatinie acid: 
VII. 625,268. 
Isoprene: 
XXIV. (pl) 1,294,662. 


Isopropyl alcohol. (See Propyl alc., Iso) 


Isovaleryl bromide: 
XXIV. (m) 998,726. 
Juglon: 
ILI. =1;327,206. 
Ketol, Methyl: 
VI. 1,024,081. 
Ketone: 
VII. 726,688. 
XXII. 1,450,569. 
Ketoxin: 
VI. 447,189. 
Lactie acid, 2-Nitro phenyl chlor: 
VII. 233,459. 
Lacto Ketone: 
2-Nitro phenyl 
VII. 540,427. 
2-Nitro phenyl methyl 
VII. 772,560. 
Limonene: 
XXIV. (pl) 1,323,589. 


Maleie acid: 


XXII. 1,401,937. 


Malonie acid: 
ester 
XXIV. . (mm) 3,400.7 127 
Anilin, diethyl ester 
VII. 620,563. 
Brom or chlor 
VII. 621,662. 
N-Dibutyl, ester 
XXIV. (m) 1,331,712. 
Diethyl 
XXIV. (m) 773,251. 


INTERMEDIATE INDEX 515 


Menthol: 
XXIV. (m) 830,043. 
Mesidin: 
XIX. 493,241. 
Metanilie acid? 
VI. 380,403; 516,381; 807,289; 
833,605; 901,675; 982,955; 
997,061; 1,093,829; 1,319,852; 
<r 1,416,621. 
- 386,709; 951,047. 
XVIII. 886,815. 


Diethyl 
VI. 625,656. 
ery ; 
- 525,657. 
Methane: ented 
XXIV. (pl) 1,408,826. 
Nitro 


XXIV. (m) 1,399,144. 

1,387,596. 
Methyl: 
she 
+ 410,739; 501,434. 

MOVE. 1,302,011. 

XXIV. (m) 610,348; 936,380; 990,310; 
1,017,699; 1,045,377; 1,059,983; 
(p) 1,316,804. 


III. 764,837. 
VIET.” ¥,2¢3,252- 
XXII. 757,058. 
XXIV. (m) 667,388; 1,419,092; 
: (p) 1,297,685. 
amin, Acetyl 
XXIV. (p) 1,434,429. 
bromide 
I. 1,473,550. 
chloride 
VI. hip hr 
XVIII. 501,4 
XXIV. (m) 38) 4488; (p) 1,434,429. 


iodide 
VI. 658,507. 
XII. 5§79,412. 
XXIV. (m) 276,796; 579,412; 936,380; 
990,310; 1,017,699. 
mercaptan 
XVIII. 325,827; 325,828. 
mercaptan, Perchlor, 
XVIII. 329,636; 329,637. 
sulfate 
VI. 381,471. 
sulfur chloride, Trichlor 
III. 1,026,588. 
Violet 
XVIII. 204,797; 331,964; 331,965. 
Methylal: (See Glycol, Dimethyl) 
Methylene: 
diresorcinol 
XV. 801,598. 
Trioxy 
XXIV. (pl) 1,429,267. 
Violet 
XV. 750,113; 755,428; 777,323- 
Mydriatin: 
XXIV. (m) 1,399,312. 
Naphtha (Crude solvert): 
XXIV. (pl) 1,297,328: 1.326,579; 
1,353,220; 1,360,665; 1,389,791; 
1,416,062; : 427,386. 
1.8-Naphthacetol 3.6-disulfo: 
VI. 620,369. 
Naphthalene: 
-JII. 188,217; 941,320; 1,374,722. 
VI. 221,116; 440,953; 456,627; 
458, 284. 
XVIII. 628,243. 
XXII. 1,431,394; 1,438,710; 1,448,688; 
1,451,666. 
XXIV. (t) 1,336,759; 1,412,949. 
1.8-Azimino, 4-sulfo 
VI. 741,552. 


1-Naphthaldehyde 2-Oxy, 3-7-disulfo: 


XVIII. 947,876. 


Naphthalene: 
aie 
- 244,757. 
Chlor 


IX. 244,757. 
XXIV. (pl) 1,455,500. 
1-Chilor 5,509 

- 644,326. 
XXIV. (t) 1,344,952. 
1-Chlor 4.8-dinitro 

XV. 675,585. 
1-Cyan, 2-sulfo 

VIL. 888,852. 
Diamino 

Viz 227,576. 

1.8- or 1.5-Diamino 

VI. 1,028,140. 
Diamino, disulfo 

VI. 558,614. 


' 2.6-dimercaptan 


VII. 1,444,277. 
1.2-Dinitro 

XV 632,570. 
1.4-Dinitro 

XV. (546,576. 
1.5-Dinitro 

III. 619,114; 619,115; 627,896; 

631,614; 633,950. 

XV. 545,336; 545,337; 667,486. 
1.8-Dinitro 

III. 627,896. 

XV. 609,327; 661,438; 674,137. 
Dinitro brom 

IX. 244,757. 
1.5-Dinitro 8-chlor 

EV. 560;3345 


Dioxy 

VI. 498,759; 566,298. 

Ke OTS, 232: 
1.4-Diox 

VI. 833,605 
1.5-Dioxy 


VI. 722,715; 722,716; 725,848; 
726,695; 741,936. 
IX. 1,412,707. 
1.6-Dioxy 
VI. 797,441. 
1.8-Dioxy 
III. 702,445. 
VI. 440,953; 502,368; 515,339; 
524,005; 644,240. 


VI. 601,859; 727,962; 933,842. 


2.7-Dioxy 

677,229; 800,914. 
XVIII. 484,697. 
1.8-Dioxy, 6-carbo 3-sulfo 

VI. 1,323,285; 1,375,701. 

1.8-Dioxy, 3.6-disulfo 

VI. 458,283; 640,010; 703,105; 
731,460; 739,118; 754,315; 
759,284; 792,032; 805,918; 
826,279; 826,280; 821,281; 
826,282; 827,468; 846,511; 
860,220; 891,931; 1,056,080; 
1,082,923; 1,087,429; 1,209,154; 
1,235,2535 1,316,718. 

1.5-Dioxy, 3-sulfo 

VI. 727,965. 

1.6-Dioxy, 3-sulfo 

VI. 664,055. 

1.7-Dioxy, 4-sulfo 

VI. 524,060. 

1.8-Dioxy, 4-sulfo, “‘S” 

VI. 417,294; 417,205; 417,296; 
423,970; 464,775; 466,202; 
468,142; 476,335; 476,336; 
476,3373 479,515; $61,615; 
567,615; 576,511; 582,958; 


516 


582,959; 602,855; 602,856; 
602,857; 603,093; 603,647; 


628,727 52 O12,3'507 41,032,402: 


2.8-Dioxy, 6-sulfo 
VI. 415,258; 863,290. 


disulfo 

VI. 456,897. 
1.3-disulfo 
XVIII. 630,224. 
1.4-disulfo 

VI. 375,848. 
2.6-disulfo 

VI. 464,566 
XVIII. 639,976. 
2.6-disulfo chloride 

VII. 1,444,277. 
2.7-disulfo 

VI. 464,135. 
XVIII. 639,977 
3.6-disulfo 

VI. §58,614. 
2.6-dithio glycolic acid 

VII. 1,444,277. 


Nitro, a-sulfo 
XG es 355030. 
Nitroso 1.8-dioxy, 2.4-disulfo 


XV. 656,631 
8-Oxy, 4-sulfo 
VI. 500,118. 
1.2.5.6-bis (oxy thiophene) 
VII. 1,444,277. 
1-sulfo 


VI. 333,035; 356,672. 

EX 2333-030, 
Tetranitro brom 

IX. 244,757. 


II. 681,613. 
4-Toluidin, 2-sulfonamid 5-sulfo 
VI. 978,438. 
1.3.8-Trinitro 
XV. 658,286. 
1.3.6-trisulfo 
x MIT. 1,321,090. 
1.4-Naphthalene diamin: 
VI. 359,576. 
1.5-Naphthalene diamin: 
VI. 718,028. 
1.8-Naphthalene diamin: 
VI. 754,856. 


XV. 1,081,598; 1,081,599; 1,081,600. 


1.4-Naphthalene diamin, Acetyl: 
Vi. 614,307. 
5 or 7-sulfo 
VI. 629,748. 


VI. 1,024,081. 
6 or 7-sulfo 
VI. 560,796. 
1.4-Naphthalene 
arylene sulfonyl: 
XXII. 1,442,818. 


diamin, aryl 


1.5-Naphthalene diamin 3.7-disulfo: 


VI. 464,566; 472,121; 473,928; 
1,169,329. 


1.8-Naphthalene diamin 3.6-disulfo: 


VI. 557,440; 562,200. 
1.2-Naphthalene diamin: 
3-sulfo 
Ns 61,03 T0256 
5-sulfo 
CUE OS 1.245 
1.3-Naphthalene diamin 6-sulfo: 
VI. 588,180; 588,181; 588,182; 


588,183; 613,642; 613,643; 
613,644; 613,646; 671,543. 
1.8-Naphthalene diamin: 
4-sulfo 
VI. 700,565; 728,021; 961,354; 
1,000,606. 
XIV. 951,046. 
5-sulfo 


VI. 716,289. 


and 


DIGEST OF PATENTS 


1-4- -Naphthalene diamin 4/-Tolyl: 
4”-oxy phenyl, 6-, 7- or 8-sulfo 
XV. 776,885. 
Naphthanthraquinone: : 


III. 798,104; 820,379; 968 
Naphthazarin: he tis 


III. 631,613; 787,824; 806,053. 


XV. 649,218; 651,122; 667,486. 
intermediate 
III. 647,370; 668,445; 756,571. 
sulfo 
III. 646,795; 646,796; 669,894. 
Naphthearbazole: 


5-Oxy 1.2-phen- 
TIT. 1,267,858: 
VII. 1,108,056; 1,108,057; 1,157,485. 
5-Oxy 1.2- -phen-, 7-sulfo, 
1,024,308. 
Naphthene: 
6-Amino oxy thio 
VII. 968,697. 
2.3-Diketo dihydro thio 
VII. 876,839. 
2-Oxy thio 
VII. 804,004; 
XIV. 1,261,858. 
3-Oxy thio 
VII. 899,994; 923,959; 941,152; 
965,170; 1,461,435. 
Thio carbo 
VII. 867,305. 
1.2-Naphthhydroquinone: 
VI. 420,372; 420,374. 
1.2-Naphthiazole; 3’-Amino phenyl 5-oxy, 
7-sulfo: 
VI. 794,568; 989,953. 
1.2-Naphthimidazole: 
VI. 873,798. 
3’-Amino phenyl dihydro 5-oxy, 7-sulfo 
VI. 912,182; 1,232,056. 
3'-Amino phenyl 8-oxy, 3.6-disulfo 
VES ered ts ae 
Amino C-phenyl 5-oxy, 7-sulfo 
VI. 1,058,562. 
3’-Amino phenyl 3-oxy, 6-sulfo 
VI. 999,230. 
3’-Amino phenyl 5-oxy, 7-sulfo 
792,600; 943,470; 1,150,656; 
1,160,406. 
4’-Amino C-phenyl 5-oxy, 7-sulfo 
VI. 837,736; 1,052,137; 1,058,692. 
3-Amino oxy phenyl, 5.7-disulfo 


894,005; 895,006. 


XXIT. 851,444. 
3-Amino phenyl, 5.7-disulfo 
XXII. 851,444. 


5-Oxy, 7-sulfo 
VI. 886,985. 
Phenyl 5-oxy, 7-sulfo 


- 933,446. 
peri Naphthindandione: 
VI. 1,233,433. 
Naphthindophenol, Oxy, sulfo: 
XXII. 16253637. 
Naphthionie acid: 
VI. 516,381; 
572,723; 
582,059; 
608,024; 
729,021 < 


558,612; 560,796; 
576,511; 582,958; 
588,182; 603,093; 
625,174; 683,190; 
754,856; 767,069; 
837,736; 843,077; 865,253; 
874,968; 989,953; 1,012,055; 
1,314,025; 1,472,333. 
1.2-Naphthisatin: 
VII. 872,227; 941,152; 
1,005,141. 


1,005,140; 
960,008; 985,767; 985,769; 
985,770. 


1,101, 770s 
1,101,778. 


985,768. 


INTERMEDIATE INDEX 517 


2-Thio 921,546; 932,289; 954,960; 
VII. 1,461,435. 955,068; 964,918; 982,509; 
Naphthoie acid: 993,549} 1,014,039; 1,023,199; 


Chlor benzoyl 


1,025,267; 1,038,884; 1,041,146; 
III. 941,320. 


1,059,670; 1,197,633; 1,233,742; 


Dioxy 1,237,192; 15,237,1933 1,314,921; 
_ VI. 493,563; 493,564; 557,437. 1,325,841; 1,342,134; 1,383,710; 
Dioxy sulfo 1,422,866. 


MiveLs 25.026. 

2-Naphthoie acid, 1.7-Dioxy 4-sulfo: 
VI. 524,070. 

Naphthoie acid: 


1-Oxy 
XVIII. 476,413. 
2-Oxy 
VI. 677,230; 743,071; 798,808; 


908,580. 
2-Naphthoie acid, 3-Oxy: 
VI. 858,065; 942,916; 983,486; 


1,034,853; 1,052,145; 1,099,108; 
1,121,026; 1,122,564; 1,215,359; 


15293,231- 
1-Naphthoie acid, 6-Oxy: 
VI. 976,401; 978,865. 
2-Naphthoie acid: 
3-Oxy anilid 
Wilwent,042,3505, 1,200,232. 
XI T LOTTI 
3-Oxy, 2/-anisidid 
Nites. 457,114. 
3-Oxy, 4’-anisidid 
BV 10) 1,415'250836 
Naphthoie acid: 
1-Oxy, disulfo 
VI. 534,573- 
Naphthol: 
VI. 1,472,334. 
1-Naphthol: 
II. 355,934- 
III. 619,115. 
VI. 204,799; Re. 9,144; 210,054; 
211,525; 211,671; 297,852; 
309,882; 310,155; 332,820; 
358,865; 501,160; 524,251; 
524,253; 524,254; 835,539; 
958,912; 1,028,006. 
VII. 961,397. 
IX. 225,108; 280,543; 324,6i5. 
XV. 648,597; 665,547; 778,477; 
821,378. 
XVII. 1,387,596. 
XVIII. 1,460,315. 
XVII. 1,387,596. 
XXIV. (t) 1,375,975. 
2-Naphthol: ; 
VI. 204,799; Re. 9,144; 210,233; 
Skt, 3505 211,525}; 211,671; 
224,928; 241,661; 251,163; 
289,613; 297,852; 302,790; 
303,335; 306,969; 389,127; 
404,097; 441,045; 512,493; 
515,704; 524,252; 525,492; 
560,392; 583,439; 584,981; 
586,865; 602,637; 602,640; 
606,436; 610,345; 625,198; 
626,933; 632,503; 634,009; 
644,237; 649,727; 649,728; 
650,757; 665,696; 667,035; 
677,227; 677,228; 677,229; 
677,230; 677,231; 680,283; 
685,647; 690,294; 692,676; 
696,811; 710,059; 714,882; 
714,883; 716,289; 718,355; 
728,388; 728,455; 728,477; 
733,280; 737,967; 749,195; 
752,562; 759,716; 765,080; 
765,581; 770,177; 779,430; 
778,476; 778,610; 787,767; 
790,363; 790,364; 803,592; 
807,422; 823,793; 842,548; 
844,814; 860,575; 865,587; 
878,964; 879,424; 880,292; 
911,186; 912,138; 914,146; 


MV, §15274,550- 
OTL rs 20'- 300510 1,901, 25041, 44054233 
1,450,990; 1,470,039. 
Naphthol, alphyl derivatives: 
XXII. 252,782. 
1-Naphthol, 4-Brom: 
VII. 958,464; 985,769; 985,770; 
1,005,140. 
2-Naphthol carbo: 
VI. 502,369. 
i-Naphthol 2-carbo: 
XXII. 1,453,659. 
2-Naphthol 3-carbo: 
DET + 935,527. 
VI. 1,003,266; 1,016,307. 
XXII. 1,450,990. 
1-Naphthol 6-carbo 3-sulfo: 
VI. 1,382,196. 
2-Naphthol 1-carbo 6-sulfonyl chloride: 
VI. 1,128,814. 
1-Naphthol: 


Chlor 

XV. 778,478. 
4-Chlor 

VII. 958,464. 
8-Chlor 


Vil 1,402,350. 
2-Naphthol, 1-Chlor: 
XXII. 1,460,774. 
1-Naphthol 8-Chlor: 
3.6-disulfo 
VI. 532,125; 535,037. 
5.7-disulfo 
XV. 620,428. 
5-sulfo 
VI. 1,408,296; 1,419,501; 1,431,655. 
2-Naphthol, 1-7-Diamino: 
XXII. 651,061. 
1-Naphthol 2.4-dicarbo: 
XXII. 1,474,928. 
Naphthol disulfo: 
VI. 483,368. 
1-Naphthol: 
disulfo 
VI. 213,563; 224,927; 418,657. 
IX. 333,036. 
3.6-disulfo 
Viies 655-0505" 500,221. 
3.8-disulfo 
XVIII. 891,888. 
4.8-disulfo 
VI. 333,035; 333,037; 333,038; 
333,039; 456,627; 456,897; 


462,824. 
XV. 611,610. 
2-Naphthol: 


disulfo 
VI. 213,563; 246,221; 249,926; 
251,164; 277,182; 285,335; 
332,830. 
3.6-disulfo 
VI. 210,233; 233,465; 250,038; 
251,163; 345,901; 396,293; 
426,345; 476,371; 500,762; 
524,069; 546,068; 546,070; 
602,540; 634,009; 644,239; 
677,227; 718,028; 757,109; 
765,079; 786,767; 787,768; 
789,096; 792,421; 820,052; 
830,312; 877,643; 888,522; 
936,951; 964,920; 1,028,493; 
1,071,832. 
XVIII. 978,801. 
oN 2105233, 
4.8-disulfo 


518 DIGEST OF PATENTS 


VI. 421,640. 
6.8-disulfo 
VI. 210,233; Re. 9,987; 251,162; 
314,938; 314,939; 332,528; 
718,389; 761,123. 
Naphthol, 4-Ethoxy: 
VII. 961,398; 961,399. 
1-Naphthol: 
8-Ethoxy, 3.6-disulfo 
VI. 797,731- 
8-Ethoxy, 5-sulfo 
VI... 13,155,765. 
4-Methoxy 
VII. 999,439. 
6-Methoxy 
VII. 1,466,687. 
Naphthol: 
1-Nitro 4-chlor 
XXII. 675,434. 
Nitroso 
VI. 807,422. 
2-Nitroso 
XVi1053,277. 
1-Naphthol: 
Nitroso 
X. 316,036; 362,835; 386,247. 
XV. 532,503. 
2-Naphthol: 


Nitroso 
X. 362,835; 548,346. 
1-Nitroso 
VI. 611,111. 
Naphthol: 
Nitroso, bisulfite 
VI. 548,416. 
Nitroso, sulfo 
X. 316,036. 
1-Naphthol, 2-Nitroso, 5-sulfo: 
1 6316,030% 
2-Naphthol, 1-Nitroso, 5-sulfo: 
X. 316,036. 
1-Naphthol: 
4-Nitro 
XXII. 675,434. 
5.6-Phen carbazole 
XIV. 1,261,858. 
Naphthol: 
sulfamino sulfo 
VI. 617,963. 
sulfo 
XXIV. (t) 1,421,701. 
1-Naphthol: 
sulfo 
. 360,972; 438,438; 447,302. 
3-sulfo 
VI. 713,507; 1,000,269; 1,010,433; 
1,020,670. 
4-sulfo 
VI. 213,564; 329,634; 357,273; 
366,078; 388,185; 440,639; 
467,162; 476,393; 493,563; 
493,583; 498,873; 500,761; 
500,762; 515,764; 516,757; 
516,758; 516,760; 534,573; 
557:436; 558,344; 620,368; 
631,089; 718,032; 759,613; 
823,703; 863,396; 1,014,5395 
1,022,612; 1,028,239; 1,097,231; 
1,169,344; 1,199,890; 1,233,742; 
1,282,356. 
IX. 333,036. 
XXII. 1,452,481. 


4- or 5-sulfo 
VI. 603,646; 605,103; 644,233; 
644,235; 644,236; 806,415. 
4-, 5- or 6-sulfo 
VI. 1,426,189. 
5-sulfo, ‘‘Cleve’s” 

VI. 333,041; 333,042; 380,927; 
476,371; 498,982; 512,493; 
802,049; 865,252; 1,235,253; 
1,237,183. 


2-Naphthol: 
sulfo 
VI. 204,799; 213,564; 242,707; 
246,272; 256,375; 256,376; 
256,377; 256,378; 256,380; 
332,829. 
1-sulfo 
IX. 256,379. 
4-sulfo 
VI. 467,162; 1,011,770. 
6-sulfo 
VI. 614,391; 628,025; 634,824; 
648,623; 654,168; 676,495; 
677,228; 680,283; 807,119; 
837,128; 888,036; 888,981; 
906,421; 989,954; 999,230; 
1,028,493; 1,071,833; 1,157,625; 
1,325,841. 
6 or 7-sulfo 
Vila 2sness. 
6 and 8-sulfo 
VI. 1,383,710. 


VI. 728,455; 1,032,412; 1,033,310. 


VI. (Ssr2,016; 
6-sulfonyl phenyl ether 
VIn> 8,123;8297 
Thio 
VII. 1,461,435. 
7-trimethyl ammonium chloride 
VI. 610,367. 
trisulfo 
VI. 268,505; 268,506; 268,507. 
1-Naphthol 3.6.8-trisulfo: 
VI. 584,081. 
XVIII. 891,889. 
Naphthol trisulfo monoamid: 
VI. 458,284. 
Naphthol Yellow S: 
VI. 844,814. 
Naphthone: 
a-Aceto 
XXIV. (m) 1,197,462. 
a-Oxy thio 
VII. 804,005. 
Naphthoquinone: 
TIT. 368,054. 
1.2-Naphthoquinone: 
III. 653,492. 
1.4-Naphthoquinone: 
III. 1,105,004; 1,396,483. 
2-3-Dichlor 
III. 1,419,502. 
7.8-Phen carbazole 
XIV. 1,261,858. 
1.2-Naphthoquinone 4-sulfo: 
wV. GI254706; 
1.4-Naphthoquinone 4’-sulfo phenyl: 
XV. 912,176. 
Naphthohydroquinone: 
VI. 420,372; 420,374. 
1.2-Naphthoxazole, 4/-Amino 
5-oxy, 7-sulfo: 
I. 1,082,596. 
Naphthyl 1-aldehyde: 
XXIV. (m) 1,197,462. 
1.2-Naphthyl 4’-Amino phenyl 3.8 disulfo, 
triazole: 
VI. 820,052. 
2-Naphthyl glycin: 
VI.. 498,803. 
Naphthyl, N-Methyl, peri-imid: 
III. 1,200,848. 
2-Naphthyl = sym-5-Oxy 
thio urea: 
VI. 697,765. 
Naphthyl: 
phenylamin 
VI. 211,671. 
sulfate 
VI. 256,401. 


phenyl 


g-sulfo, phenyl 


apt shin 


INTERMEDIATE INDEX 


1.2-Naphthyl  4/-Sulfo 
triazole: 

VI. 670,398. 

Naphthylamin: 

II. 134,076. 

VI. 204,799; Re. 9,144; 221,116; 
221,119; 242,707; 251,164; 
260,242; 261,175; 261,766; 
er hy 2851335; 289,613; 
396,293; 844,845. 

XXII. 1,449,423. 
1-Naphthylamin: 

ELE t. 018,43 35 

-VI. 204,799; Re. 9,144; 256,376; 
297,852; 332,528; 345,901; 
365,666; 365,667; 380,402; 
380,928; 402,980; 412,440; 
423,569; 425,585; 438,438; 
440,639; 449,629; 462,415; 
. 462,824; 464,566; 464,775; 
466,202; 473,928; 476,336; 
476,393; 479,515; 482,106; 
491,410; 500,118; 502,912; 
503,148; 512,167; 515,339; 
515,381; 533403; 543,747; 
543,748; 548,416; 560,796; 
 §82,959; 590,088; 593,790; 
601,033; 602,641; 603,093; 
605,103; 608,999; 610,349; 
613,638; 613,640; 613,644; 
613,920; 618,963; 628,025; 
629,748; 634,824; 644,234; 
644,237; 644,238; 644,239; 
644,240; 654,107; 654,168; 
655,529; 671,896; 683,120; 
877,643; 899,171; 903,284; 


phenyl 


1,014,539; 1,033,310; 1,073,905; 
1,113,468; 1,180,985; 1,183,831; 
1,193,829; 1,265,031; 1,310,532; 
1,319,852; 1,416,621; 1,452,083. 
XIV. 051,046; 951,047; 951,049. 
XV. 741,030; 796,443; 1,099,039; 
1,251,369. 
XVIII. 297,413; 688,967. 
XXII. 1,442,818; 1,451,666. 
2-Naphthylamin: 
III. 1,011,068; 1,016,638; 1,162,496. 


VI. 320,633; 333.2573 365,666; 
365,667; 380,402; 381,045; 
381,046; 395,474; 497,032; 
558,612; 606,436; 1,024,794; 
1,217,042; 1,362,936. 
X. 1,455,488. 
XIV. 350,230. 
1-Naphthylamin, Acetyl 4-amino, 6 or 7- 
sulfo: 
VI. 1,422,866. 
2-Naphthylamin, 4/-Amino 2’-sulfo phenyl: 
VI. 628,025. 
1-Naphthylamin : 
Benzyl 
XVIII. 406,435. 
Benzyl, 8-sulfo 
VI. 722,860. 
2-Naphthylamin, 1-Chlor, 5-sulfo: 
VI. 710,059. 
1-Naphthylamin: 
2-diazo oxid 4-sulfo 
VI. 1,028,006. 
2.4-Dichlor, 7-sulfo 
VI. 765,581. 
Naphthylamin: 
disulfo 
VI. 345,901. 
3.6-disulfo 
VI. 412,440. 
1-Naphthylamin: 
disulfo 
VI. 502,912; 888,852. 
2.4-disulfo 
VI. 770,177; 933:447- 
3.6-disulfo 
: VI. 546,068; 546,069; 935,018. 
4.7-disulfo 


3.6-dioxy .; 


519 


VI. 376,392; 420,374; 449,629. 
4.8-disulfo : 
Viv srr, 532: 


2-Naphthylamin: 


disulfo 
VI. 454,648. 
1.5-disulfo 
VI. 718,356. 
3.6-disulfo 
VI. 454,840; 468,539; 594,123; 
631,611; 740,768; 842,048; 
959,078; 1,051,859; 1,052,031; 
1,067,881. 
4.8-disulfo 
VI. 931,424; 976,4013 1,180,985; 
1,183,831. 
XIV. 951,046; 
1-Naphthylamin: 
4-Ethoxy phenyl 
XVIII. 658,504. 
Ethyl oe 
1,113,766; 1,199,697. 
XVIII. 517,473. 
2-Naphthylamin 
Ethyl 
-sulfo 


VI. 
Ethyl, 5 
V 451,132. 


1-Naphthylamin, Methyl pheny]: 
XVIII. 308,748; 684,457. 
2-Naphthylamin, Methyl phenyl: 
XVIII. 603,016. 
1-Naphthylamin, Methyl, sulfo: 
VI. 381,471. 
2-Naphthylamin: 
1-Methyl, sulfo 
VI. 696,811. 
Methyl, 7-sulfo 
. 1,009,740. 
Naphthylamin, Nitro: 
Vis e2LI 525s 
1-Naphthylamin: 
4-Nitro 
XXII. 675,434. 
4-Nitro, 6- or 7-sulfo 
VI. 1,371,979. : 
Naphthylamin, Nitroso dimethyl: 
Nou A 2O.S TT. 
1-Naphthylamin: 
4-oxy phenyl 
XV. 1,105,515. 
4’-Oxy phenyl 4.8-dinitro 
XV. 675,585. 
Naphthylamin, Phenyl: 
XV. 778,478. 
1-Naphthylamin, Phenyl: 
XVIII. 297,414. 
2-Naphthylamin, Phenyl: 
VI. 1,457,235. 
1-Naphthylamin: 
Phenyl, 5- or 7-sulfo 
- 887,348. 
Phenyl, 8-sulfo 
498,405; 611,664; 841,371; 


951,047. 


449,629; 499,216; 921,105. 


1,188,421. 
2-Naphthylamin, Phenyl, 6-sulfo: 
VI. 989,001. 


Naphthylamin sulfo: 
VI. 261,175; 262,620; 289,613; 


447,303. 
i-Naphthylamin: 
sulfo 
204,799; Re. 9,144; 286,376; 
268,506; 358,865; 363,502; 
375,848; 380,928; 381,471; 
412,149; 421,640; 447,302. 
XIV. 386,709. 
a-sulfo 
IX. 333,036. 
2-sulfo 
VI. 619,194; 1,016,307; 1,113,468. 
XV. 1,083,489. 
XVIII. 506,918. 


520 DIGEST OF PATENTS 


XXII. 1,083,489. 
4-sulfo (See Naphthionic acid) 
sa 


XVIII. 
6-sulfo 
VI. 603,645; 603,646; 603,647; 

603,648; 644,238; 676,494; 
676,495; 920,151; 999,7973 

1,000,269; 1,010,433; 1,024,080; 
Dertrate 1,032,412; 1,099,676; 
1,180,985; 1,270,290; 1,319,852. 
XIV. 951,047. 
6- or 7-sulfo 

VI. 498,404; 498,405; 536,870; 
543,539; 583,439; 602,856; 
602,857; 602,858; 603,090; 
644,233; 644,235; 644,236; 
648,623; 658,697; 679,221; 
709,186; 716,342; 722,860; 
1,014,884; 1,416,621; 1,422,866. 


874,967; 1,054,348. 
605,119. 


XIV. 951,047. 
7-sulfo 
VI. 546,068; 546,069; 546,070; 
920,151; 1,038,209; 1,038,210; 
1,088,735; 1,125,050; 1,270,290. 
8-sulfo 


VI. 498,404. 
2-Naphthylamin: 
sulfo 
VI. 204,799; Re. 9,144; 256,378; 
257,243; 332,830; 334,257; 
342,432; 344,971; 357,274; 
401,483; 404,331; 476,336; 
690,294. 
XVIII. 263,420. 
VI. 650,757; 858,065; 911,186; 
1,073,784; 1,383,711. 


VI. 498,303. 
XIV. 386,709. 


VI. 329,634; 1,101,739. 
VII. 1,108,056. 


6-sulfo 
VI. 332,829; 420,372; 1,092,842; 
1,394,823. 
7-sulfo 


VI. 362,813; 363,502; 395,474. 


VI. 555,658; 908,580; 1,429,782. 
1-Naphthylamin: 


Tetrahydro 
DOV ceed I Ss 230s 
4'-Tolyl 
VI. 425,885. 
XVIII. 647,260. 
2-Naphthylamin: 
3-Tolyl 
XVIII. 688,966. 
4-Tolyl 


VI. 354,746; 423,550. 
1-Naphthylamin, 4’-Tolyl, 8-sulfo: 


VI. 408,404. 
Naphthyiamin trisulfo: 
VI. 458,284. 


2-Naphthylamin, 1.5.7-trisulfo: 
VI. 737.967. 
Nicotinic acid chloride: 
XXIV. (m) 1,403,117. 
2-Nitranilin: 
VI. 888,981; 1,188,545. 
3-Nitranilin: 
VI. 341,991; 380,927; 528,965; 
889,016; 950,404. 
XV. 805,637; 896,916; 897,873; 
909,277; 1,405,446. 
XXIV. (pl) 1,441,598. 
4-Nitranilin: 
VI. 211,525; 333,257; 334,257; 
376,392; 380,928; 424,019; 


Oil: 


454,648; 480,326; 483,368; 
491,410; 514,599; 525,657; 
537,532; 536,878; 536,879; 
536,880; 557,440; 562,200; 
563,384; 588,203; 606,438; 
613,639; 613,645; 639,040; 
639,041; 647,237; 700,565; 
728,388; 728,455; 843,808; 
1,006,051; 1,076,756; 1,082,719; 
1,235,253; 1,241,153; 1,365,040; 
1,415,704. 
IX. 763,756. 
XV. 706,969; 1,199,697; 1,251,369; 
1,302,671. 
XXII. 729,876; 1,400,555. 
2-Nitranilin: 
4-Chlor. 
VI. 990,173; 1,059,599. 
IX. 955,080. 


VI. 914,146; 1,075,305. 

IX. 932,266. 
4-Nitranilin, 2-Chlor: 

VI. 628,233; 703,105; 865,587; 

943,536. 
2-Nitranilin: 
4.5-Dichlor 

VI. 921,546. 

4-sulfo 

VI. 692,675, 1,086,155. 
3-Nitranilin, 4-sulfo: 

VI. 993,549. 
4-Nitranilin : 

2-sulfo 
VI. 714,882; 724,743; 740,767; 
800,914; 832,393; 921,105; 
921,239; 944,328; 991,750; 
1,008,907; 1,038,209; 1,038,210; 
1,088,7353 1,123,430. 
3-sulfo 
VI. 687,171. 
2-sulfon, ethyl anilid 
VI. 1,429,781; 1,429,782. 
Nitranisol: 
VI. 357,273. 
Nitration: 
XXII. 800,913; 1,297,170; 1,309,320; 
1,423,494. 
Nitrobenzene: 

III. 893,837. 

VI. 406,669; 406,670. 

VII. 841,456; 848,355; 867,715; 

887,609; 899,863; 968,697. 

IX. S1,306;008. 

XVIII. 310,128; 471,638; 707,813. 
2-Nitrobenzene, 1.4-Dichlor: 

XV. 658,055. 

Nitrobenzene, 3.4-Dichlor: 

VI. 787,767. 
4-Nitrobenzene sulfo: 

XV. 718,342. 

Nitrovenzene 2.4.5-Trichlor: 

XV. 1,329,898. , 
Nitrosobenzene: (See Benzene, Nitroso.) 
Nitrophenetol: 4 

VI. 342,432. i 
Nitrosamin, 4-Amino methyl phenyl: 

VI. 754,315- 

Novolak resin: 
XXIV. (pl) 1,354,154. 


XXIV. (pl 1,430,034. ¥ 

Hydrocarbon 

XXII. 1,477,058; 1,477,7293 1,478,027. 

Mineral, sulfo 

XXII. 1,301,662; 1,301,663; 1,303,779; 
1,330,624. 

Pelargonium 

XXIV. (f) 548,719. 

Sulfo salt of resin F i 


INTERMEDIATE INDEX 521 


AAI. 722,506; 722,507. 
Soluble 


XXII. 628,503; 861,397; 1,301,662; 
1,301,663; 1,303,779; 1,330,624; 


1,416,284. 
Turkey Red 
VI. g11,186. 


Olefin: 
XXIV. (pl) 1,430,538. 
Orchil, Methyl: 
VI. 412,148; 412,149. 
Orein (Orcinol): 
394,425; 404,331; 410,058; 
509,623. 
Methyl, sulfo 
VI. 410,057. 
Oxalie acid: 
XVIII. 603,300; 609,599. 
XXII. 1,445,162. 


XXIV. (m) 837,083; 942,674; 1,028,074. 


Oxalyl chloride: 
III. 1,126,475. 
VII. 1,461,435. 
Oxamin sulfo, 3-Amino tolyl: 
VI. 683,190. 
Oxanthrol: 
III. 818,992. 
Oxidation: 
XXII. 729,502; 757,136; 823,435; 


1,308,796; 1,324,715; 1,332,028. 


Patent Blue, amino leuco: 
VI. 1,237,192; 1,237,193. 
Perimidin: 
VII. 1,222,790. 
pe Va 01,802,271 % 1,132,022. 
Methyl 
XV. 1,209,580. 
Perylene: 
XXII. 1,384,615; 1,454,204. 
Dioxy 
XXII. 1,454,204; 1,454,205. 
Petroleum: 
XXIV. (e) 1,309,577; (m) 318,662; 
513,204. 
Phenacetin: 
XXIV. (m) 596,797. 
Phenanthraquinone, 4.5-Dinitro: 
Vn eT, 007,514. 
Phenanthrene: 
III. 1,288,431. 
XXII. 685,895. 
quinone 
JTIl. 644,333. 
quinone, Dibrom 
III. 1,095,780. 
2-Phenanthrol: 
Wile 3025270. 
Phenazin: 
XV. 701,435. 
2-Amino 7-oxy 
XV. 818,980. 
Naphsultam 
VI. 1,431,656. 


PTY ok, 4 56,502. 
4-Phenetidin: 
MPV. 951,046. 
XXIV. (f) 489,728; (m) 543,579; 
596,797; 602,109; 602,690. 
Phenetidin, N-Methyl: 
XXIV. (m) 1,426,348. 
4-Phenetidin, 2-Nitro: 
VI. 569,395. 


Phenmorpholin: 

XIX. 949,906. 
Methyl 

XX 2O13,514. 
Phenol: 


III. 619,114; 831,002; 1,038,589. 


Vie oin TOs 2Tr, 5255. 211,075; 
297,852; 386,192; 426,345; 
454,840; 472,121; 501,160; 
514,599; 515,897; 519,522; 


519,523; 543,539; 585,104; 
627,679; 628,233; 644,462; 
655,013; 880,293; 1,009,952; 
1,014,633; 1,067,881. 

IX. 1,380,186. 

[XeENO TS e232 

XIV. 350,229; 350,230; 455,952. 

XV. 646,873; 653,277; 653,278; 
679,199; 696,751; 698,555; 
706,969; 708,662; 723,154; 
740,465; 763,320; 776,264; 

779,860; 1,083,110. 

XVIII. 603,300. 

XIX. 1,381,503. 

XXII. 679,199; 776,264; 779,860; 
1,301,909; 1,308,757; 1,309,683; 
1,312,127; 1,365,407; 1,409,588; 
she SE e PAas 593: Bes 
1,439,128; 1,461,745; 1,466,991. 

XXIV. (e) 1,292,266; (m) 812,608; 4 
942,674; 948,084; 966,820; 
1,432,291; (pl) 1,088,677; 
1,088,678; 1,310,087; 1,310,088; 
1,345,694; 1,369,352; 1,374,526; 
1,375:959; 1,398,146; 1,429,265; 
1,429,267; 1,435,801; 

(t) 1,399,510. 
alphyl derivatives 

XXII. 252,782. 


Amino 
XXII. 618,809. 
2-Amino 
VI. 826,279; 1,282,356. 


XV. 608,355} 650,326; 934,302. 


- 402,980. 
XIX. 675,215; 821,452. 


VI. 476,335; 548,460; 1,219,954. 

XIV. 636,065; 951,046. 

XV. 549,036; 594,107; 601,363; 
601,364; 610,541; 628,607; 
635,168; 636,066; 645,738; 
648,957; 748,755; 650,292; 
650,293; 650,326; 650,327; 
657,768; 658,055; 660,058; 
667,689; 675,585; 688,646; 
695,835; 709,151; 731,669; 
73557753 741,030; 796,443; 
841,877; 843,156; 866,939; 
909,155; 1,081,600; 1,083,489; 
1,102,171; . 1,113,766; 1,175,230; 
1,209,580; 1,265,836; 1,265,837; 
1,314,929. 

XXII. 595,807; 641,100; 648,755; 
650,327; 709,151; 1,083,489. 
4-Amino, allyl ester 
XOX EV Gin) 1,394,037. 
Acetyl 3-amino 
XIX. 821,452. 
Acetyl 4-amino 
VI. 749,193. 
Acetyl 2.5-diamino 4-chlor 
VI. 759,284. 
Acetyl 2.4-diamino, 6-sulfo 

VI. 803,592; 983,132. 

Acetyl 3.6-diamino, 4 sulfo, methyl ether 

VI. 1,408,405. 

Acetyl ethyl 4-amino 

SOXTVe a) 5 7.05410- 

4’-Amino benzoyl 2-amino 4-chlor 
VI. 1,114,750. 

3-Amino carbo 

XXII. 427,564. 

4-Amino 5-carbo 
VII. 881,158. 

2-Amino 4-chlor 

VI. 644,238; 826,280; 843,756; 
863,290; 958,774; 1,034,898; 
1,221,849. 

XV OSL.07 7. 

4-Amino 2-chlor 
XV. 732,090; 742,189. 


522 


XXII. 742,180. 


s-Amino 4-chlor acetyl 2-amino, methyl 


ether 
IT. 1,169,344. 
2-Amino 4-chlor, 6-carbo 
I. 1,375,701. wees 
2-Amino 4-chlor, ethenyl derivative 
I. 843,077. | 
2-Amino 6-chlor 4-nitro 
VI. 961,354; 981,276; 1,408,206. 
2-Amino 4-chlor, 6 sulfo 
VI. 672,714; 683,120; 685,647; 
726,695; 865,252; 1,003,266; 


1,078,925. 
6-Amino 2-chlor, 4-sulfo 
VI. 644,239. 


2-Amino dichlor 
» 302,790; 303,335. 
4-Amino dichlor : 

XV. 1,081,598; 1,081,599. 

2-Amino 4.6-dichlor 

1,419,501. 
Amino dinitro 
XXII. 1,460,708. 
4-Amino, ditoluene disulfo ester 
XXIV. (p) 1,316,804. 
2-Amino seleno 
XXIV. (m) 1,087,157. 
2-Amino, 4-sulfamid 

VI. 1,325,841. 

2-Amino, 4-sulfanilid 
VI. 1,316,781. 
Amino, sulfo 

VI. 516,381; 726,963. 
Amino, sulfo’ III 

VI. 671,903. 
Amino, sulfo IV 

VI. 671,902; 671,904. 

2-Amino, sulfo 

VI. 1,265,031. 

2-Amino, 4-sulfo 

IT. 923,635. 

VI. 634,824; 722,715; 727,962; 
727,965; 727,967; 729,601; 
961,355; 964,919; 1,210,908; 
1,216,760; 1,216,812; 1,419,500. 

XV. 644,959. 

XXIV. (m) 466,708. 
2-Amino, q-sulfo, methyl ether 

VI. 1,453,660. 

2-Amino, 6-sulfo 

VI. 865,252; 865,253. 

3-Amino, 6-sulfo 

VI. 572,723; 946,052; 1,025,983. 

4-Amino, 2-sulfo 

XV. 628,609; 648,754; 650,292. 

XXII. 648,754. 
2-Amino thio 

XV. 1,452,805. 

Benzylidene 4-amino 
XXIV. (p) 922,040. 
Chlorinated, esters. 
XXII. 1,023,758. 


2-Chlor 
XV. 776,264. 
XXII. 776,264. ’ 
4-Chlor 


Vi; 036,327. 


Chlor amino derivatives (See Phenol, 


Amino chlor) 
6-Chlor 2.4-dinitro 
XV. 935,009. 
Chlor nitro 

V. 701,051. 
4-Chlor 2-nitro 

VI. 683,119. 
4-Chlor 2-nitro, 6-sulfo 

VI. 684,065. 
2.4-Diamino 

VI. 823,793. 

XV. 618,152. 
2.4-Diamino, 6-sulfo 

VI. 693,670. 


DIGEST OF PATENTS 


2.6-Diamino, 4-sulfo 
VI. 665,606; 677,231; 680,283; 
692,676. 
2.6-Dichlor 
XVIII. 978,800. 
fs eae thio 
I 1,044,674; 1,044,675. 
3-4-Dichlor thio ie 

III. 1,044,673. 

Diethyl 3-amino 
XVIII. 701,427. 

XIX. 377,349; 377,350; 402,436; 
573:299; 576,222; 576,223; 
609,998; 625,641. 

Dimethyl 3-amino 
XIX. 425,504; 445,684; 449,520; 
578,578; 1,006,738. 
Dimethyl 4-amino 
XXIV. (p) 1,434,429. 
Dinitro 

XV. 702,369; 904,224; 1,026,881; 

1,187,614; 1,279,307. 


2.4-Dinitro 
IX. 1,299,171; 1,349,802; 1,393,714; 
1,413,914. 


XV. 618,152; 647,846; 655,659. 
Ethyl 3-amino 
456,081; 633,883. 
Ethyl benzyl 3-amino 
xX 609,998; 624,877. 
Halogen 


XXIV. (m) 1,036,087. 
2-Halogen 
XXII. 554,974. 
4-Methyl acetyl 2-amino 
VI. 1,408,363. 
Methyl 4-amino 
XXIV. (p) 1,434,429. 
Methylene amino 
XXIV. (pl) 1,354,154. 
2-Nitro 
XV. 960,652. 
XXIV. (m)_ 1,390,972. 
4-Nitro 2-amino 
VI. 644,240; 841,371; 843,137; 
879,552; 933,842; 1,159,375; 
T,213,0755. 2 216,813; 1,242,536; 
1,259,499; 1,282,354; 1,202,385; 
1,411,245. 
s-Nitro, 2-amino 
II. 1,416,646. 
VI. 827,468; 1,265,030; 1,394,823. 
2-Nitro 4-amino, 6-sulfo 
VI. 644,235. 
2-Nitro 6-amino, 4-sulfo 
VI. 628,814; 644,233; 644,234; 
644,237; 671,902; 671,903; 


787,046. 
3-Nitro 2-amino, 5-sulfo 
VI. 647,236. 


4-Nitro 2-amino, 6-sulfo 
VI. 644,236; 986,287. 
6-Nitro 2-amino, 4-sulfo 
VI. 654,064; 654,065; 667,035; 
677,227; 677,228; 677,229; 
677,230; 695,238; 725,848; 
727,064; 727,966; 741,552; 
798, 808; 1,027,132. 
6-Nitro 2-amino, 4-sulfonamid 
VI. 1,338,414. 
s-Nitro 4-chlor 2-amino 
VI. 843,077; 846,511; 933,841. 
6-Nitro 4-chlor 2-amino 
VI. 843,149; 1,011,770. 
2-Nitro, 4-sulfo 
IX. 300,874. 
XXIV. (m) 466,708. 
Nitroso 
XV. 919,572; 1,081,638; 1,083,489; 
1,128,371; 1,471,854. 
XXII. 1,083,489. 
4-Nitroso 


INTERMEDIATE INDEX 


XV. 653,278; 727,387; 802,049; 
829,740; 931,598; 956,348; 
966,002; 1,247,475; 1,329,898; 


1,465,853. 
3-sulfo 

1,126,656. 
4-sulfo 

879,552. 


IX. 300,874; 1,396,001. 
XXII. 1,465,680. 
4’-Toluidin 3’-sulfonyl 4-chlor, 6-sulfo 
Vile or 529,234: 
3-4.5-Trichlor 2-amino, 
VI. 1,408,297; 1,431,655. 
3-4.6-Trichlor 2-amino 
VI. 1,426,189; 1,426,190. 
Phenolphthalein: 
XXIV. (m) 618,167; 998,726. 
Diethyl 3-amino 
XIX. 642,893. 
Tetra iodo 
XXIV. (m) 618,168. 
Tetramethyl 3.3’-diamino 
XIX. 499,927. 
Phenosafraninone: 
XV. 778,713. 
Phenthiazole: 
4-Amino phenyl, carbo 
1,125,073. 
4’-Amino phenyl, carbo sulfo 
Ty 4,128,074. 
Phenyl acetic acid: 
259,629. 
eeetee 
- 259,629. 
chloride 
VII. 1,043,682. 
Phenyl: 
2-Amino 4-chlor, ether 
T. 950,404. 
2-Amino, ether 
VI. 932,813. 
3-Amino 4-oxy, arsenic acid 
XXIV. (m) 1,120,700. 
2-Amino, 2’-tolyl ether 
VI. 932,812. 


3-Amino, trimethyl ammonium chloride 


VI. 602,641; Re. 11,714. 
chloroform: 
XVIII. 1,460,315. 
cyan acetamid 


XXIV. (m) 1,285,703. 


4.4/-Di- (See 4.4’-Diphenyl and deriva- 


- tives) 


sym-Diethyl diamino ditolyl oxy, methane 


VIII. 472,001. 
Dimethyl diamino tolyl, methane 
I. 675,568. 
dimethyl ammonium chloride 
XV. 688,999. 
ethyl oxy acetamid 
XXIV. (m) 1,375,949. 
hydrazin 
fis > 5,001,325. 
VII. 1,108,056. 
XXIV. (m) 307,399. _ 
4-Methoxy, cinchonic acid 
XXIV. (m) 1,076,160. 
Methyl amino, propanol HCl 
XXIV. (m) 1,356,877. 
mustard oil 
VI. 607,765. 
2-Nitro, nitro methane 
VII. 1,015,495. 
3-Nitro 4-oxy, arsenic acid 
XXIV. (m) 1,422,294. 
sulfonyl chloride 
VI. 1,067,881. 
4’-Sulfo 2,4-diamino, ether 
VI. 880,292. 
thio glycocol 2-carbo 
VII. 868,295. 
34 


4’-Tolyl 4-amino, sulfid 
VI) 99 ,076;321- 
Tolyl 4-amino, sulfoxid 
1,077,492. 
Trioxy, carbinol 
XVIII. 609,598. 
Phenyl glycin: 
DUD 1,23,39070.1,200, 103; 
VII. 704,804; 714,000; 714,042; 
727,270; 731,285; 737,836; 
761,440; 756,171; 776,884; 
798,077; 818,341; 839,099; 
860,900; 894,579; 960,671; 
963,377; 984,442; 1,211,413; 
Re. 14,364. 
Acetyl 


VII. 801,708. 
Acetyl, arsenic acid 
XXIV. (m) 1,299,215. 
3-Amino 
VI. 858,444; 8593930; 1,056,493. 
Amino, sulfo 
VI. 658,506. 
Arseno 
XXIV. (m) 1,290,214; 1,315,127. 
4-Arseno, bis=(3’-oxy anilid), 
OUD Ven (nt) 2,305.1 27. 
2-carbo 
VII. 618,096; 647,263; 868,755. 
4-Brom 3-chlor, 2-carbo 
VII. 957,683. 
4-Brom 6-chlor, 2-carbo 
VII. 948,241. 
3.4-Dichlor, 2-carbo 
VII. 955,410. 
5-Ethyl thio, 2-carbo 
Vito 1.001.457. 
Phenyl glycocol: 
VII. 524,256; 622,139; 680,395; 
778,752. 
2-carbo 


VII. 546,165; 625,268; 690,346; 
730,148; 761,007; 778,725. 

2-carbo, diethyl ester 

VII. 651,453. 
2.3-dicarbo 

VII. 540,564. 
sulfo IIT 

VIO 671,003: 


VI. 671,902; 671,904. 
Thio, 2-carbo 
VII. 891,690. 
Phenylene diamin: 
VI. 384,342; 491,422. 
2-Phenylene diamin: 
XV. 641,935. 
3-Phenylene diamin: 
II. 800,785; 992,947. 
VI. 211,525; 341,991; 344,075; 
365,409; 440,288; 462,414; 
465,116; 502,912; 515,381; 
516,203; 516,380; 525,245; 
526,763; 536,431; 5574375 
558,612; 560,448; 560,449; 
561,694; 561,709; 572,723; 
575,904; 578,580; 595,021; 
603,009; 615,497; 619,503; 
619,518; 628,814; 638,127; 
647,236; 647,237; 679,221; 
683,190; 717,550; 748,076; 
832,393; 936,456; 946,050; 
946,051; 971,112; 982,508; 
987,417; 988,000; 997,061; 
999,558; 1,012,619; 1,019,3215 


1,023,120; 1,028,306; 1,052,647; 
1,078,926; 1,082,581; 1,150,825; 


1,209,154; 1,327,688. 
XV. 635,169; 695,835; 801,508; 
904,809; 909,152; 909,153; 
909,156. 
3 or 4-Phenylene diamin: 
VI. 858,444. 


523 


524 


4-Phenylene diamin: 
II. 298,998; 387,097; 863,761; 
992,947; 1,105,554; 1,326,367. 
211,671; 511,688; 512,167; 
560,448; 561,694; 615,497; 
620,574; 638,127; 640,010; 
644,462; 679,221; 858,444; 
936,450; 963,739; 999,558. 
455,952; 636,065. 
594,106; 594,107; 
608,354; 641,587; 
646,873; 708,662; 
764,734; 782,905; 
820,501; 904,809; 
1,083,110; 
1,440,833. 
(Ab) 1,277,056; 


VI. 


XIV. 
XV. 601,363; 
641,588; 
764,733; 
813,643; 
958,640; 
1,083,489; 1,129,574; 


XXIII. 1,350,600. 
Acetyl 
VI. 526,763; 528,721; 561,700; 

631,089; 648,623; 654,167; 
654,168; 658,897; 662,122; 
748,076; 859,930; 1,000,606; 
1,363,886; 1,365,040; 1,372,439. 
Acetyl 2-chlor 
7 731,460. 
as-Acetyl ethyl 
Cate iter ¢ 
3-Phenylene diamin: 
acetyl, 4-sulfo 


1,201,544. 
3'-Amino benzoyl 
VI. 2,362,936. 


4-Phenylene diamin: 
3’-Amino benzoyl 
VI. 1,153,555. 
Benzoyl, 3-sulfo 


VI. 936,951. 
3-Phenylene diamin: 


4-Chlor 
VI. 657,064; 1,014,982; 1,014,984. 
5-Chlor 
VI. 657,065. 
4-Phenylene diamin, 2.6-Dichlor: 
XV. 779,860. 
XXII. 770,860. 
3-Phenylene diamin: 
Di-formyl 
XV. 720,874: 
as-Dimethy]l, 
1,455,486. 
4-Phenylene diamin: 
Dimethyl 
XV. 679,199; 698,555; 763,320; 
776,264. 
XXII. 679,199; 776,264. 
as-Dimethy 
2 567,055 2 1%, 206,232: 
XV. 696,751; 728,623; 776,264; 
778,478; 821,378. 


3-Phenylene diamin: 
2.4-Dinitro 6-chlor 4'-4”-dioxy diphenyl 


XV. 688,646. 
4.6-Dinitro 2’4”-dioxy diphenyl 
650,326. 
4'.4”-Dioxy 3'.3”’-dicarbo diphenyl 4.6- 
dinitro 
XV. 648,753. 
4’.4”-Dioxy diphenyl 4.6-dinitro 
V.. 648,755. > : 
4’.4”-Dioxy 3’.3”-disulfo diphenyl 4.6- 
dinitro 
XV. 648,754. 
Phenylene diamin disulfo: 
VI. 778,610. 
3-Phenylene diamin: 
disulfo 
VI. - 524,261; 524,202 631,010; 
1. 8592930- 
2.5-disulfo 
VI. 906,422. 


as-Ethyl dimethyl 
X. 1,455,487. 
Formyl 


DIGEST OF PATENTS 


VI. 971,111; 971,112; 1,052,647. 
Formyl, 4-sulfo 


VI. 999,944. 


VI. (972,112: 
4-Phenylene diamin: 


2.6-disulfo 
VI. 1,474,587. 
Methyl 
VI. 754,315. 
3-Phenylene diamin: 
Nitro 
VI. 545,333; 568,549; 611,663; 
631,610; 631,011; 995,160; 
1,051,859. 
4-Nitro 
VI. 964,919. 
3/-Nitro benzoyl 
VI. er i8saias 
4-Phenylene diamin: 
4’-Nitro 
VI. 941,088. 


3-Nitro acetyl 
VI. 792,032; 792,033% 


. gm Iste retara es, 
4’-Nitro benzoyl 


792,034; 


VI. 941,088 
3/-Nitro benzoyl, 3-sulfo 
VI, 1,104,824. 
Nitro diacetyl 
XV. 738,027. 
Oxalyl 
VI. 999,797; 1,125,050. 


Oxalyl, sulfo 


VI. 1,078,926; 1,150,656. 
oxaminic acid 
VI. 1,009,745. 
3-Phenylene diamin: 
sulfo 
VI. 656,120; 658,506; 658,507; 
1,009,952. 
4-sulfo 
VI. 946,050; 963,739; 1,026,984. 
4-Phenylene diamin: 
sulfo 
XXII. 798,807. 
3-sulfo 
ITT. 1,106,422: 
VI. 687,171; 936,051. 
4'-tolyl sulfone 
VI. 1,359,969. 
3-Phenylene diamin, Trimethyl ammon- 
ium: 


VI. 602,637; 602,638; 602,639; 
602,640; 617,544; 626,913. 
Phloroglucin: 
XXIV.  (m) 1,120,700. 
Phosgene: 
ITT. 
VI. 


1,025,195; 1,038,003. 
430,533; 430,534; 430,535; 
662,122; 663,408 607,171; 
935,016; 939,017; 935,018; 
978,580; 986,287; 999,944; 
1,001,183; 1,006,051; 1,006,920; 
1,024,031; 1,032,797; 1,052,135; 
1,076,756; 1,087,427; 1,087,428; 
XV. 1,081,508. 
XVIII. 290,856; 327,953; 333,861; 
501,434. 
XXIV. (m) 501,235; 1,308,071. 
Phrenthrene, Oxy-thio, carbo: 


VII. 888,852. 
Phthalamin: 
VI. Vert T80: 
sulfo derivatives 
VIL 21280; 
Phthalein: 
XIX. 1,054,247. 
Phthalie acid: 
XIX. 413,048; 990,224. 
XXII. 708,171 


Amino 


Se ines ns, 


ee et Tee 


INTERMEDIATE INDEX 525 


VI. 297,852. 
3-Amino 

VII. 540,564. 
Dichlor 

XIX. 413,049. 
Tetra chlor 


XIX. 413,050. 

anhydride 

III. 902,895; 1,055,287; 1,196,127; 
1,355,100. 

WE. 2,421,245. 

XV. 688,885. 

XIX. 377,349; 377,350; 456,081; 
516,585; 576,222; 576,223; 
578,578; 609,997; 609,998; 
633,883; 1,381,503. 

OX D Lets 255,517.7 1,301,309313330,1923 
1,444,068; 1,465,689. 
XXIV. (pl) 1,424,137. 


anhydride 2-Chlor 
THI 4 55520. 
anhydride 4-Chlor 
TII. 929,442. 
anhydride, Tetra chlor 
XXII. 322,368. 
Phthalimid: 
Wie 1,322,052. 
XIX. 821,452. 
RALTV.. Gn) 621,319. 
Phthaloperinone: 
XV. 1,592,445; 1,126,630. 
Dinitro 
XV. 1,081,602. 
Phthaloyl chloride, Tere-: 
TIT. 1,459,536. 
Picramiec acid: 
583,439; 624,256; 627,783; 
646,711; 657,064; 657,065; 
658,506; 658,507; 664,955; 
671,904; 704,826; 740,767; 
740,768; 807,289; 906,421; 
924,232; 936,321; 987,362; 
1,155,765; 1,199,233; 1,190,234; 
1,217,042; 1,219,054; 1,281,243; 
1,310,532; 1,408,363. 
XXII. 1,460,708. 
Picric acid: 
Mis 221 11s. 
XXII. 1,472,791. 
Picryl chloride: 
XALV: (m) 1,087,157. 
Pinene: 
XXIV. 
Piperazin: 
XXIV. (m) 709,321. 
Piperonal: 
XXIV. (m) 886,085; (p) 1,326,973. 
Polysaccharids: 
XV. 909,151; 909,152; 909,153. 
Primulin: 
VI. ,440,288; 524,261; 524,262; 
656,120; 914,144; 1,107,164. 


(m) 1,411,859; (p) 1,323,589. 


sulfo 
XII. 656,857; 656,858; 656,859; 
658,593. 
sulfo, Xylidin 
XIV. 951,048. 
Propiolie acid, 2-Nitro phenyl: 
VII. 227,470; 228,300; 233,458; 
233,460; 235,193; 240,359; 
250,035; 250,036; 251,499; 
251,671; 259,260; 259,261. . 
N-Propyl alcohol: 
XXIV. (m) 950,936. 
Propyl alcohol: 
Diallyl amino 
XXIV. (m) 1,388,573. 


Iso- 

XXIV. (m) 1,412,937. t 
a-Methyl b-methyl y-dimethyl amino 
XXIV. (m) 1,474,567. 


Protocatechuic aldehyde: 


XXIV. (m) 1,399,144. 
Diacetyl 
XXIV. (m) 1,399,144. 


Purification: 
XXII. 

Purpurea: 
XXIV. 

Purpurin;: 


IIT. 509,425; 623,638; 749,913. 


(Sepn. of Crudes.) 
722,336; 1,339,310; 1,409,588. 


(m) 1,391,705. 


sulfo 
III. 779,825. 
Pyranthrone: 
III. 955,105. 


Pyrazole anthrone: 
III. 1,329,435. 
Pyrazolone: 
VI. 844,845; 1,216,813. 
3’-Amino phenyl, carbo 
VI. 936,367. 
Amino 1-phenyl, 3-carbo 
VI. 639,042. 
3-Amino phenyl, carbo 
1,094,448. 
4'-Amino phenyl 2.4-dimethyl 3-oxymethyl 
XXIV. (m) 936,380. 
3'/-Amino phenyl methyl 
VAL Inia 7 Sos: 
4’-Amino phenyl methyl 
NV lieu t. t 23.2036 
4’-Amino phenyl 2.3.4-trimethyl 


XXIV. (m) 990,310. 
Aryl methyl 
XII. 935,830. 


4’-Brom phenyl 2.3-dimethyl 

2 (in)! 1,053,240. 

2'-Carbo phenyl methyl 
VI. 1,338,506. 

2’-Chlor aryl methyl, sulfo 
XII. 1,098,600. 

2’-Chlor phenyl methyl 
Vie 31,047,016; 41,100,471- 

2’-Chlor phenyl methyl, 3-sulfo 
XII. 982,050. 

2'-Chlor phenyl methyl, 4-sulfo 
XII. 1,098,600. 

2’-Chlor phenyl methyl, 5-sulfo 
XII. 1,098,600. 

2'-Chlor s’-sulfo phenyl, carbo 
VI. 1,084,363. 

2’-Chlor 4’-sulfo phenyl methyl 

1,172,061. 

5’-sulfo phenyl methyl 
Vike 0272244 0el FAO hea te 

Dehydro thio sulfo tolyl methyl 
VI. 1,114,844. 

21.5 /~ Dichlor phenyl methyl 
Wola she ,09T, 148. 

2h! -Dichlor 4'-sulfo, phenyl methyl 


OVI. gor, 675. 
Dimethyl 4’-amino phenyl 2.3-dimethyl 
XXIV. (m) 680,278; 686,998; 686,999; 
768,398. 
4'.8/- Disuifo 2- aonthes methyl 
VI. 902,186: 
Nitro oxy phenyl methyl 
VI. 1,210,898. 
4-Nitro phenyl, carbo 
XII. 627,690. 
4'-Nitro phenyl methyl 
XII. 988,870. 
4’-Nitro phenyl 2.3.4-trimethyl 
4XXI I. 990,310. 
Phenyl 
VI. 739,069. 


XII. 808,919. 
Phenyl dimethyl 
(m) 674,686; 674,687. 
Phenyl 2.3-dimethyl 4-amino 
(m) 579,412; 1,056,881. 
Phenyl 2.3-dimethyl 4- -sulfamino 
(m) 1,347,083. 
Phenyl ethyl 


526 DIGEST OF PATENTS 


XII. 464,861; 1,026,257. 

XXIV. (m) 464,861. 

Phenyl methyl (1- Phenyl 3-methyl 5-pyra- 
zolone) 

VI. 602,638; 791,524; 791,525; 
980,521; 983,132; 984,900; 
999,797; 1,001,286; 1,014,114; 
1,021,304; 1,021,365; 1,024,080; 
1,032,433; 1,183,831; 1,193,829. 

XII. 656,857; 731,670; 808,919; 
1,026,257. 

XVIII. 1,023,977. 

Phenyl 3.4.4-trimethyl 

XXIV. (m) 1,017,699. 

Sulfo aryl methyl 

XII. 935,829; 935,830. 
s’-Sulfo 3’-carbo 2’-oxy phenyl methyl 
VI. 1,270,325; 1,286,411; 1,338,397. 
4'-Sulfo phenyl, carbo 
VI. aie ek 839,605; 849,690; 
849, 
XII. 656, 58: 656,859; 93553703 
935,830; 1,010,919. 
4’-Sulfo phenyl methyl 
VI. 959,109; 971,761; 971,762; 
995,160; -1,021,366; 1,199,233; 
1,199,234. 
XII. 656,859; 935,829; 935,830. 

Sulfo tolyl methy 

- KIT. 935,830. 

4-Tolyl dimethyl 

XXIV. (m) 503,066. 

Pyridin: 
XV. 661,907. 
XIX. 913,514. 


XXII. 1,290,124; 1,414,441; 1,416,205; 
1,416,206. 
XXIV. (f) 464,772. 


Amino benzy 
VI. 1,087,427. 
4’-Amino benzyl 
VI. _ 1,073,754; 1,074,946. 
Amino benzyl, chioride 
VI. 626,933. 
Pyridinium chloride, 2’.4’-Dinitro phenyl: 
XIX. 913,513. 
Pyrimidin: 
4-Imino 2.6-dioxy 
XXII. 811,826; 811,827. 
Alkyl 4-imino 2.6-dioxy 


XXII. 811,828; 811,829. 
4.5-Dinitro 
INS Veer ear bere 
2-Oxy 
XXII. 848,791. 
Pyrocatechol, Methyl amino aceto: 
XXIV. (m) 1,423,101. 
Pyrogallie acid: 
VI. 548,460. 
Pyrogallol: 
III. 443,402. 
Wik (220,lids 
XVIII 478,005. 
XIX. 1,055,864; 1,194,380. 
XXII. 1,434,593. 
XXIV. (p) 767,815. 
disulfo 


XIX. 1,106,185. 


XX.) 1,003;257 
Pyroracemie acid: 
MI.) 257,812; )257,013. 
XXIV. (m) 1,197,462. 
Pyruvie acid: 
XXIV. (m) 1,138,936. 
Quinaldin: 
XXII. 309,035. 
hydro base 
XXII. 316,249. 
Methoxy and ethoxy 
XXII. 316,248. 
Tolu- 
XIII. 780,741; 805,143. 


Quinazolin, 2.4-Dioxy: 
VEO Ver. OLr2ons: 
Quinie acid: 
XXIV. (m) 690,804. 
Quinicin, Phenyl methyl oxy: 
XXII. 348,483. 
Quinizarin: 
III. 599,426; 599,427. 


Quinol: 
XXII. 1,322,580. 
Quinolin: 
XXII. 241,738. 
XXIV. (m) 273,498; 254,098; 282,488; 
1,063,099. 


5-Amino 8-ethoxy 


XXIV. (m) 512,590. 
Chlor iod 
XXII. 332,358. 


Dihydro iso-, derivatives 
XXIV. (m) 1,437,802. 
2.4-Dimethyl 6-ethoxy, ethiodide 
XIII. 1,437,674. 
1.5-Dioxy 
VI. 806,077. 


VI. 1,052,031; 1,073,754; 1,074,946. 


VI. 914,144; 924,232; 961,355. 
8-Methoxy 2-phenyl, 4-carbo 


XXIV. (m) 1,045,377; 1,045,378. 
Methyl 
XXII. 268,543. 
6-Methyl 2- -phenyl, 4-carbo 
XXIV. (m) 1,045,379; 1,045,759. 
Oxy 
XXII. 237,917; 237,918; 270,045; 
906,918. 

XXIV. (m) 466,708. 
2-Oxy 
XXIV. (m) 563,116; 906,918. 
4-Oxy 

VI. 558,613. 
8-Oxy 


VI. 1,419,500. 
Oxy hydro ethyl 
XXIV. (m) 273,498. 
8-Oxy, 5-sulfo 

VI. 1,405,687. 
2-Phenyl, 4-carbo 


MAILTO FT 07558 72, 

XXIV. (m) 1,076,160; 1,086,881; 
1,091,870; 1,306,439; 1,336,9525 
1,378,3433 1,434,306. 

sulfo 

XXIV. (m) 276,796; 1,408,462. 


Tolu-, methyl iodide 
XIII. 805,143. 
Quinone: 


III. 1,046,498; 1,052,520. 


XV. $23,138 Re. 11,050. 
XXIT. 71,328,631; 1,322,500: 
chlorimid 

XV. 1,440,681. 
dianili 


III. 1,009,981. 
3.6-Dichlor 2.5-dianilino 


. ATES O28: 
4’.5”-Diphenetidino dichlor 
II 1,065,063. 
Reduction: 
XXII. 256,330; 691,132; 700,671; 
700,672; 714,428; 736,204; 
736,205; 736,206; 738,404; 
742,797; 1,345,589; 1,358,324. 
Resorcinol: 
769,715. 


VI. 211,525; 260,359; 297,852; 
361,404; 384,342; 399,581; 
452,197; 509,623; 515,100; 
516,381; 571,933; 572:7233 
615,497; 626,913; 946,052; 
969,450; 983,805; 1,023,120; 
1,074,429; 1,082,924; 1,082,925; 


INTERMEDIATE INDEX 527 


1,087,430; 1,090,379; 1,125,050; AALV (mM). 1,183,711: 
¥5020,400;  13150,8253 1,1535555; Ethyl tolu- 
1,169,329; 1,173,077; 1,180,985; XV. 829,740. 


1,185,413; 1,232,056; 1,365,706; Salicyl aldehyde: 


1,422,866. XVIII. 866 
. 9359. 
& 615,232. MAI. 1,380,277: 
XV. es 630,952; 801,598; Salicyl thio acetic acid: 
1,319,052. 


XVIII. 501,434. 


XIX. 596,333; 609,997; 1,055,885. 
XXII. 1,314,138; 1,406,745; 1,446,550; 


1,446,551. 
XXIV. (m) 966,820. 
alphyl derivatives 
XXII. 252,782. 
Chlor 5 
XIX. 990,224. 
Dinitroso 
ds 413,724. 
Nitro, disulfo 
XIX. 1,055,885. 
sulfo 
XIX. 1,002,825. 
1.2.4-Resorcylie acid: 
VI. 528,965; 1,437,758. 
Nitro 
XIX. 1,055,885. 
Retene: 
VI. 1,395,238. 
Retenequinone: 
XIV. 386,709. 
Rhodamin: 
XIX. 489,923; 645,78. 
Diethyl 
XIX. 516,584; 613,926; 641,184. 
Diethyl benzyl 
XIX. 645,781. 
Diethyl homo 
XIX. 516,585. 
.2’ or 4’-Ditolyl 
XIX. 438,053. 
Tetra ethyl 
XIX. 516,588; 646,794. 
Tetra methyl 
XIX. 516,589. 
as-Rhodamin: 
XIX. 584,119. 
Dialkyl 
XIX. 675,215. 
Trimethyl, ethyl ether, 
IDX, 043,371. 
Rhodol: 


Dimethyl, ethyl ether, 
WA © O13, 113. 
Dimethyl, methyl ether, 
625,536. 
Dimethyl, sulfo 
XIX. 1,055,864. 
sulfo 
XIX. 1,106,185. 
Rosanilin: 
XVIII. 32,965; 43,066; 204,798; 
250,247; 262,680; 421,049. 
Resindulin: 
Phenyl, sulfo 
524,221; §24,222. 


XV. 796,443. 
Rosolie acid: 
XVIII. 589,766; 591,309. 
Safranin: 
VI. 524,251; 524,254; 649,728. 


VI. 649,727. 


VI. 524,252; 524,253. 
Dimethyl pheno- 

VI. 1,032,433. 
Tolu- 


Salicylie acid: 
III. 


VII. 831,844; 836,309; 841,008; 
848,354; 848,355; 850,827; 
867,305; 867,715; 887,609. 
Acetyl 4-amino, 
VII. 867,306; 872,585; 968,697. 
Acetyl 5-amino 
VII. 881,157. 
4-Chlor 
VII. 915,346. 


476,491; 957,125; 999,785. 
VI. 221,118; 329,638; 329,639; 
375,930; 380,067; 396,294; 
398,990; 399,581; 401,024; 
401,634; 406,670; 424,019; 
430,533; 430,535; 431,207; 
476,393; 479,515; 493,583; 
503,148; 514,931; 515,897; 
516,468; 535,036; 536,878; 
555,359; 555,058; 567,413; 
588,183; 602,858; 603,090; 
603,646; 603,647; 603,648; 
606,439; 608,024; 613,643; 
613,644; 622,961; 628,721; 
631,089; 638,127; 640,010; 
666,867; 678,323; 679,974; 
713,507; 718,028; 718,032; 
724,894; 818,981; 902,186; 
943,536; 949,633; 959,109; 
971,762; 974,346; 991,750; 
995,161; 1,009,745 1,024,308; 
1,075,134; 1,099,676; 1,126,489; 
1,157,169; 1,264,604; 1,282,356; 
1,310,532; 1,474,587. 
XIV. 350,229. 
XV. 909,154. 
XVIII. 410,739; 476,414; 603,300; 
609,599; 877,053. 
XIX. 1,403,888 
XXII. 1,380,277 
XXIV. (m) 503,066; 680,278; 830,043; 
922,995; 1,338,297; (f) 1,427,400. 
benzyl ester 
XXIV. (m) 1,436,304. 
ethyl ester 
XXIV. (m) 563,993. 
Acetyl 
XXIV. (m) 811,884; 1,058,904; 1,063,099; 
1,181,485; 1,321,307; 1,431,863 
Acetyl, benzyl ester 
XIV. (m) 1,436,304. 
Amino 
VI. 438,438; 514,931; 546,070. 
XV. 648,753. 
XXII. 648,753. 
2-Amino 
VI. 818,981. 
4-Amino 
VI. 452,197; 464,775; 502,368; 
502,369; 509,623. 
XIV. 636,065. 
XV. 628,608; 701,435. 
4-Amino, methyl ester 
XXIV. (m) 619,549. 
3’-Amino 4’-anisoyl 4’amino 
Wis 31,007,230. 
6-Amino 4-chlor 
VI. 716,342. 
Amino sulfo 
VI. 655,529. 
2-Amino sulfo 
VI. 1,282,356. 
2-Amino 4-sulfo 
VI. 1,234,894. 
Anilino 


528 DIGEST OF PATENTS 
XIX. 1,403,888. Sulfobenzid, 3.3'-Dinitro 4.4’-diamino: 
chloride IX. 1,166,808. 
XL Ve Gm) 915075,5S0. Sulfonation: 


Dinitro 

XV. 711,038. 
6-Methyl 4-amino 

Wis et,1 4.7 70s 
5-Nitro 
XXIV. (m) 563,993. 
4-Nitro 6-Amino 

VI. 704,825; 704,826; 907,999. 
5-Nitro 3-amino 

VI. 1,382,196. 
4'-Nitro phenyl 
XXIV. (m) 492,868. 
Oxy, methyl ester 


XXIV. (m) 880,171. 
sulfo 
XXIV. (t)_ 1,344,950. 


shee and derivatives (See Thio salicylic 
acid. 
Sodamid: 

VII. 680,395; 704,804; 722,793. 
Stearie acid: 

VI, 002,021: 
Stearic acid anilid and derivatives: 

(See Anilid, Stearic acid.) 


Stilbene: 
4”-Amino benzoyl 4’-amino benzoyl di- 
amino, disulfo 
VI. 1,059,670. 


VI. 360,792; 456,628; 456,897. 
3.3’/-Diamino dibenzoyl diamino, disulfo 
VI. 1,082,924. 
Diamino dimethyl, sulfide 
VI. 418,657. 
4.4'-Diamino, 2.2’-disulfo 
XIV. 350,229; 350,230; 360,553. 
Dinitro, disulfo 


VI. 903,284. 
Dinitro, 2.2’-disulfo 
XVIII. 668,580. 


4.4'-Dinitro, 2.2'-disulfo 
ALVe 350,220; 350,230; 
Suceinie acid: 


XXIV. (m) 1,439,605. 
dibenzyl ester 
XXIV. (m) 1,439,605. 
anhydride 
Le aa 252504. 
XXII. 821,201. 
XXIV. (m) 768,562; 821,291. 
dialdehyde 
XXIV. (m) 1,419,092. 
Sulfanilie acid: 
Ill. 644,333; 707:373; 740;913; 
754,768; 779,825; 787,824. 
VI. 210,054; 225,908; 253,598; 
269,359; 277,182; 285,335; 
309,882; 333,041; 399,581; 
425,885; 466,202; 468,142; 
Biz FiOS eh TOs 22 hed.cOns 
524,665; 543,747; 543,748; 
590,088; 593,347; 593,790; 
606,439; 618,963; 644,334; 
719,048; 728,388; 741,936; 
798,098; 903,284; 912,182; 
932,812; 935,016; 978,580; 
1,020,756; 1,078,503; 1,078,504; 
1,106,781. 
IX. 666,627. 
XIV. 386,709; 951,047; 951,049. 
XV. 601,364; 601,365; 608,354; 
608.3555 712,176: 
XXIV. (m) 602,646. 
2-Sualfanilie acid: 
WE. (920,053 5 1,125,873. 


XXII. 88,979; 1,300,227; 1,300,228; 
1,301,360; 1,301,785; 1,321,994; 
1,332,203; 1,390,241; 1,396,320; 
1,422,564. 
Suprarenin HCl: 
XXIV. (m) 1,472,298. 
Tannie acid: 
XXIV. (m) 533,718; 598,914; 607,172; 
658,747; 659,204; 1,183,711. 
Tar bases: 


XXII. 1,339,310. 
Tartaric acid: 
XXIV. (m)e 2,423, to" 
XxX. Obs 2325 
Dioxy 


XII. 324,630; 935,370; 969,428; 
972,951; 1,010,919; 1,109,919. 
Tartronie acid, Amino phenyl: 
XVILIS “707. 6mae 
XXIV. (m) 676,850. 
Tetrazotie acid, Amino: 
XXII. 546,604. 
Theobromin, sodium: 
XXIV. (m)_ 1,414,333. 
Thiazin, 4.4’Dioxy: 
XV. 6012464: 
Thiocarbanilid: 
VII. 647,281. 
XXIV. (pl) 1,422,506; 1,477,805. 
Thionapthene derivatives: (See Naph- 
thene, Thio.) 


Thiophene: 
XXII. 1,085,708. 
XXIV. (m) 1,350,408. 


1.2-Naphthoxy 
VII. 1,434,983. 
Naphthalene 1.2.5.6-bis=oxy- 
VII. 1,444,277. 
Thio salicylie acid: 
TII. 1,007,104; 1,026,621; 1,065,102. 
VII. 850,827; 867,679; 943,560; 
943,561. 
XXII. 943,560. 
w-Dichlor vinyl 
VII. 910,839. 
Ethylene bis- 
VII. 949,592. 


VII. 804,004. 
Thio teluidin derivatives: 
Thio.) 
Thymol: 
XXII. 
Tolidin: 
VI. 329,632; 329,633; 363,502; 
375,848; 375,930; 381,132; 
394,425; 394,841; 395,634; 
401,024; 412,149; 416,145; 
417,207; Re. 11,1793; 417,296; 
462,415; 462,824; 468,049; 
468,539; 408,759; 506,284; 
515,807; 516,381; 516,756; 
516,759; 519,523; 521,005; 
534,5733 544,700; 601,859; 
602,855; 602,856; 602,857; 
606,436; 613,646; 619,503; 
620,369; 639,042; 670,398; 
832,3933 959,109; 974,3463 
1,281,938; 1,383,710. 
2.2'-Folidin: 
VI. 366,678; 498,873; 501,118; 
516,604; 516,758; 521,985; 
541,859; 556,298; 585,104. 
2.3’/-Tolidin: 
VI. 429,350. 
3.3/-Tolidin: 
VI. 971,761; 971,762; 995,161; 
1,071,832; 1,071,833. 
Tolidin, Diisopropyl: 
VI. 1,314,925; 1,314,926. 


(See Toluidin, 


1,449,121. 


ae ee ee 


ere <«z 


ee ee ee ee eee 


we og 


it 


* 


INTERMEDIATE INDEX 


1.2-Toloxazin: 
Ill. 729,073. 
Toluene: 
III. 929,442. 
Vive 3845356. 
VII. 259,629. 
XVIII. 603,016; 688,967. 


we rePea tee245049% (3,334;0333 1533953173 
1,365,849; 1,419,124; 1,430,585; 


1,458,491. 


XXIV. (£) 319,082; 551,131; 648,568; 


692,598. 
Amino azo 
XXIV. (m) 1,076,840. 
Amino azo, sulfo 
XIV. 951,047. 
iV te 0,397.5) 201,707. 
2-Chlor 
III. 902,895. 
XXII. 902,895. 
4-Chlor 2-nitro 
VII. 677,239. 
5-Chlor, 3-sulfo 
XII. 935,370. 
3.3/-Diamino azoxy 
Wile i323'2,056. 
2.4-Dinitro, 6-sulfo 
XV. 606,193. 


2.4-disulfo 
MIS, 7,292;050. 
2-Nitro 


Wit. 673,887. 
Mew 145 0,715. 


VI. 360,792. 
DEL Vin 3'51052 202) 350,230; 
XVIII. 541,572. 
2-Toluene 4-Nitro, sulfamid: 
XXIV. (£) 692,863. 
Toluene: 
4-Nitro 2-sulfo 
XIV. 350,229; 350,230; 360,553; 
395,115; 396,527; 455,952 
601,063; 636,065; 951,046; 
951,047; 951,048; 951,049. 
XVIII. 688,580. 
4-Nitro, sulfo 


VI. 644,462. 
XV. 1,053,676. 
sulfamid 


XXIV.- (f£) 319,082. 
sulfinic acid 

PUT 1,261,858. 
Pelee 407 57 Ves 
XXIV. (f£) 667,861. 


XXII. 602,682. 


VIDS} 772,500. 
Vo 608,220. 
XVIII. 673,632. 
XXII. 1,292,950. 
4-sulfo chloride 
VI. 800,914. 
XVIII. 866,350. 
XXII. 1,442,818. 
AALVe (£). 319,082. 
(m) 603,195. 
sulfone anilid 
VI. 1,042,198. 
Trinitro 
1,268,803. 


XXIV. (e) 1,297,524; 1,309,5593 
1,450,675. 
4-Tolaiec acid: 
SN aie t 3 1O0;7'5 0. 
Toluidin: 
III. 688,576. 
bei 333503055) 300,192) 
VII. 955,699. 
XIV. 613,911. 
XVIII. 501,434. 


529 


2-Toluidin: 
VI. 211,671; 406,669; 406,670; 
524,251; 719,049; 792,600; 
794,568; 813,155; 837,736; 
989,953; 1,006,929; 1,022,612; 
1,024,308; 1,338,397. 
VIL. 627,652: ¥,243,771. 
XII. 1,098,600. 
XV. 709,151; 742,189; 958,640. 
XVIII. 471,638; 473,453; 647,834. 
XIX, 605,781. 
XXII. 709,151; 742,189. 
3-Toluidin: 
VI. 602,637; 602,638; 602,639; 
610,345; 617,544; 626,933; 
1,028,140; 1,029,639; 1,051,859; 
1,052,031; 1,073,902; 1,087,428; 
I,149,575- 
XVIII. 688,967. 
4-Toluidin: 
III. 509,426; 599,427; 603,659; 
608,338; 640,986; 654,294; 
654,295; 656,081; 666,594; 
666,702; 673,691; 675,572; 
675.5733 675,574; 675,575; 
687,657; 687,658; 688,645; 
690,292; 715,662; 722,719; 
723,125; 734,325; 734,866; 
738,614; 764,837; 778,036; 
812,599; 932,290; 1,026,557 
1,070,196; 1,078,505; 1,131,516; 
1,207,702: 
VI. 211,671; 498,404; 675,632; 
1,065,950. 
VII. 310,604. 
XII. 935,829; 1,098,600. 
XVIII. 423,341; 995,494; 1,218,232; 
1,244,149. 
NXT. 722,710; 3,441,055. 
XXEVG (m) 1,138,936: 
2-Toluidin, Acetyl 4-amino: 
XXII. 902,150. 
Acetyl, 4-sulfo 
I. 935,371. 
Acidyl, 5-sulfo 
XII. 935,370. 
Toluidin, Amino azoxy: 
Wile 25003762. 
2-Toluidin, Azoxy: 
Vin (505,764. 
3-Toluidin, Azoxy: 
Vii 036,367. 
2-Toluidin formaldehyde Anhydro: 
XVIII. 471,638. 
2-Toluidin, Benzyl: 
XVIII. 567,567. 
Benzyl azimino 
= -903,020- 
Benzyl, disulfo 
XVIII. 580,188. 
Benzyl, sulfo 
XVIII. 580,186. 
4-Tolaidin: 
3-Chlor 
VI. 765,069; 765,080. 
5-Chlor 2 nitro 
VI. 1,038,884. 
2-Toluidin: 
3-Chlor, 5-sulfo 
XII. 935,370. 
6-Chlor, 4-sulfo 
VI. 935,371; 1,027,148. 
3-Toluidin: 
4-Chlor, 6-sulfo 
VI.” 733,290. 
6-Chlor, 4-sulfo 
VI. 083,486. 
4-Toluidin, 3-Chlor, 6-sulfo: 
VI. 759,716. 
2-Toluidin: . 
3-Chlor 5-sulfo, hydrazin 
XII. 935,370. . ‘ 
4-Chlor, xanthogenic acid 


530 DIGEST OF PATENTS 


VII. 906,029. 
Tolunidin, Dehydro thio: 
VI. 428,629; 515,339; 524,005; 
5324793 535,037; 543,539; 
588,180; 1,159,386. 
XV. 802,455. 


Acetyl 
VI. 1,125,073. 
sulfo 
XII. 658,593. 


XIV. 951,048. 
4-Toluidin, Dehydro thio, sulfo 
VI. 398,990; 404,097; 441,945. 
Toluidin 2.2’-disulfo: 
VI. 1,264,604. 
3-Toluidin, 4-Ethoxy: 
IV. 1,452,083. 
4-Toluidin, 3-Ethoxy: 
VI. 987,362. 
2-Toluidin, Ethyl: 
XV. 732,090. 
XVIII. 472,091. 
4-Toluidin, Ethyl: 
VII. 619,884. 
3-Toluidin: 
Ethyl benzyl 
AV ELT st, 218,292: 
Ethyl sulfo benzyl 
XVIII. 1,101,770. 
Ethyl 4’-sulfo benzyl 
VI. 1,054,348. 
4-Methoxy 
VI. 1,209,154. 
4-Toluidin, 5-Methoxy 2-nitro: 
VI. 1,038,884. 
Toluidin, Methyl: 
b a2Oa ts: 
2-Toluidin: 
Methyl 
XVIII. 519,071; 525,627. 
Methyl, sulfo 
XVIII. 580,187. 


Toluidin: 

Nitro 
Viveetis25. 

3-Nitro 
VI. 380,927. 


2-Teluidin, 
nitro.) 
2-Toluidin, 5-Nitro (NH,=1): 
VI. 500,761; 954,960; 1,034,853; 
1,052,145; 1,122,564; 1,215,359. 
IX. 763,756; 763,765. 
4-Toluidin, 3-Nitro, (NH,=1): 
VI as 2647T 35 01,8 o3s370° 
IX. 763,765. 
YToluidin: 
Nitroso dimethyl 
X. 420,311. 
sulfo 
VI. 211,671; 333,042; 466,841. 
XII. 935,830. 
4-Toluidin sulfo: 


4-Nitro: (See 


VI. 428,629. 
2-Tolnidin: 
4-sulfo 


XII. 935,830; 1,098,600. 
XIV. 386,709. 


5-sulfo 
XII. 935,830; 1,098,600. 
XM VIEL. '538;027- 


4-Toluaidin 3-sulfo: 
VI. 743,071; 849,690. 
XII. 935,830; 935,870; 1,098,600. 
XIV. 350,229; 386,709. 
XXII. 1,441,655. 
2-Toluidin s-sulfo 2/-anisidid: 
VI. 1,005,233. 
Toluidin sulfon anilid: 
VI. 978,439. 
4-Tolnidin 2-sulfon anilid: 
VI. 965,882; 989,954. 


2-Toluidin, 5- 


Tolyl 3-aldehyde: 
VII. 662,073; 662,074; 662,075. 
4.6-Dichlor 
XVIII. 1,042,493. 
Nitro 
VII. 662,076. 
sulfo 
XVIII. 
2-sulfo 
XXII. 709,159. 
4-Toluyl, 3-Nitro, chloride: 
XXIV. (m) 1,317,251. 
Toluylene diamin: 
VI. §24,251; 1,314,922. 
2.6-Toluylene diamin: 
VI. 1,000,606. 
3-Toluylene diamin: 


709,160. 


(1.3.4-NH,. NH,. 


II. 739,071. 

VI. 365,409; 375,930; 395,634; 
516,604; 541,750; 582,958; 
602,857; 608,024; 620,574; 
639,041; 671,543; 688,478; 
718,032; 971,III; 999,713. 

XV. 640,559; 688,885; 712,747; 
714,542; 722,630; 723,448; 
782,905; 813,643; 829,740; 
895,637; 896,916; 934,302; 
934,303; 1,165,531; 1,251,388; 
1,251,389; 1,327,688. 


XXII. 829,740. 
4-Tolaylene diamin: (1.4.3-NH,. NH,,. 


CH,.) 
VI. 221,120; o16:923- 
XIV. 636,065. 
XV. 641,589; 641,953; 641,954; 
7731346; 866,939. 
Toluylene diamin: 
Acetyl 
XV. 785,675. 
4-Toluylene diamin, as- Ethyl benzoyl: 
VI. 1,199,890. 
3-Toluylene diamin, Formyl: 
I. 1,455,486; 1,455,487; 1,455,488. 
Toluylene diamin sulfo: 
XV. 746,926. 
2.4-Toluylene diamin 6-sulfo: 
VI. 516,380. 
2.6-Toluylene diamin 4-sulfo: 
VI. 465,116; 407,032; 558,612; 
558,614; 568,549; 588,614; 
639,040; 644,291; 644,292; 
982,507; 982,508; 1,123,263. 
3-Toluylene diamin sulfo: 
VI. 619,503; 748,076. 
3-Toluylene diamin 5-sulfo: 
VI. 1,006,929; 1,024,031; 4,052,647% 
1,183,378. 
3-Tolaylene diamin 6-sulfo: 
VI. 603,090; 946,051. 
3-Toluylene diamin 4-tolyl sulfonamid: 
VI. 704,825; 704,826. 
Toluylene di-urea: 
XV. 760,110. ; 
2-Toluyliec acid, 4-Chlor 6-nitro: 
VII. 892,897. 
Tolyl: 
3-aldehyde 
VII. 276,889; 276,890. 
5-aldehyde 
VII. 276,890. 
Tolylamin, 2.4-Dinitrophenyl oxy: 
XV. 660,067. 
2-Tolylamin, 3’-Oxy phenyl: 
XIX. 609,997. 
4-Tolylamin, 3/-Oxy phenyl: 
XVIII. 501,434. 
Tolylamin, Phenyl oxy: 
XV. 660,097. 
2-Tolyl glycin: 
VII. 746,065. 


q 

+ 

i] 

i 
e 

. 
vd 
ia 
% 


INTERMEDIATE INDEX 531 


2-Tolyl glycocol: 
VWilie 617,052; 619,883; 621,652. 
4-Toly!I glycocol carbo, diethyl ester: 


Vinyl acetate: (See Acetic acid, vinyl ester.) 
Violanthrene, Iso: 
III. 1,003,268. 


VII. 644,326. Xanthine. 3.7-Dimethyl: 
4-Tolyl sulfonamid, 1-Naphthol: XXIV. (m) 1,415,700. 
XV. 843,156. Xanthogenie acid: 
Trimethyl arsen, or ethyl deriv: VII. 867,305; 872,085; 877,743; 
XXIV. (m) 1,308,413. 881,157; 881,158; 881,159; 
Triphenyl carbinol: 892,897; 916,030. 
Dimethyl 3-amino tetramethyl 4-diamino 4-Chlor 2-toluidin (See 2-Toluidin 4- 


XVIII. 437,089. 


pia Chlor xanthogenic acid) 
3-oxy tetramethyl diamino, disulfo 


Xanthone, 5-Amino anthraquinone 1.2-phen 


XVIII. 463,898; 490,408. thio: 
Triphenylimethane: III. 999,785. 
3-Amino tetraethyl diamino Xylene: 
XVIII. 412,614; 453,477. XXIT. 1,311,848; 1,434,593. 
Diamino Amino azo 
Vi, 1,160,471; 1,172,061. VI. 246,221. 
3-Nitro diamino Amino azo, sulfo 
Ea OO Ley. VI. 256,378. 
3-Oxy UF teteasthy! diamino, disulfo w-Tetra or hexachlor 
XVIII. 1,478,015. XIV. 1,459,536. 
3-Oxy tetramethyl diamino, disulfo 3-Xylene: 
XVIII. 615,472. VII. 276,880. 
4-Toluidino dimethyl dioxy, dicarbo XVIII. 1,219,166. 
XVIII. 1,244,149. XXII. 1,477,058. 


Triphenyl stibine dibromide: 


2.4-Xylenol, 6-Amino: 


2.4-Xylidin 6-sulfo: 


Waleryl bromide, Iso: TI ot 447,658, 
XXIV. (m) 998,726. 3-Xylidin 6-sulfo: 
Vanillin: VI. 839,605; 933,562. 
XXIV. (f) 1,138,936; 1,329,272; Yohimbin: 
(m) 1,138,936. XXIV. (m) 1,305,462. 


XXIV. (m) 1,060,765. VI. 826,281. 
Uramil, 1.3.7- Trimethy1: sym-Xylenol 2-carbo: 
XXIV. (m) 667,388. XVIII. 1,034,173. 
Urea: Xylidin: 
III. 928,891; 1,004,107. VI. 210,233; 211,671; 277,182; 
VI. 935,016. 333,035; 418,657; 456,627; 
XXII. 1,173,550; 1,274,503; 1,292,019; 456,897; 677,516. 
1,326,045; 1,344,673; 1,369,383; XIII. 677,517. 
1,417,277; 1,419,157; 1,429,483; XIV. 613,911. 
1,429,953. 2.4-Kylidin: 
XXIV. (m) 773,251; 1,331,712. VII. 881,624. 
Dimethyl diphenyl XXII. 1,441,655 
ALIS "3,393,597. 2.6-KX ylidin: 
Di or tetra alkyl diaryl VI. 656,620; 1,084,363. 
XXII. T,307,5 70. 3-Xylidin: 
5.5’-Dioxy 7.7’-disulfo 1.2’-dinapthol VI. 916,161; 1,073,903. 
XXII. 675, 630. : sym-3-Xylidin: 
5.5’-Dioxy 7.7’-disulfo 1.2’-dinapthol thio XVIII. 676,555. 
AXII,, © 675,631. 4-Xylidin: 
5.5’-Dioxy 7.7’-disulfo 2.2’-dinaphthyl thio VI. 591,616; 602,540; 877,644; 
XXII. 653,678. 931,424; 933,447; 933,448; 
5.6’-Dioxy 7.8’-disulfo 2.2’-dinaphthyl thio 033,562; 943,470; 1,020,756; 
XXII. 675,628. 1,092,842; 1,180,985. 
Urethane: Xylidin: 
Ethyl Dehydro thio 
XXIV. (m) 1,424,236. XII. 658,593. 
4-Oxy phenyl ethyl Ethyl 
. XXIV. Fie 537,841; 541,489. View2515163- 
ps-Urie acid Nitro 
XXIV. (m) 667,388. VI. 231,925: 
Urie acid, 1.3.7-Trimethyl: Rarer heats: Tepes 
Mem E 7g Sen) 867,358. 2.4-Xylidin, 6-Nitro: 
Uvitie acid: VII. 881,159. 
Oxy Xylidin Primulin sulfo: (See Primulin.) 
asa 488,290. Xylidin sulfo: 
7 XIV. 386,709. 
VI. 493,413. ott. 


PATENTEE INDEX. 


The names in this index are arranged alphabetically, with state or country of 
origin of patentee, abridged name of assignee, and patent numbers by dye groups. 


(For key to column 3 see Assignee Index.) 


Prefixes such as von, de or du, considered as part of the name, determine its — 
Names employing the umlaut are arranged as though the vowel 
For instance, Konig is placed as though 


alphabetical order. 
were followed by the indicated letter e. 
spelled Koenig. 


Letters in parentheses before patent numbers, last column, indicate the sub- 


divisions of groups XXIII and XXIV, as follows: 


XXIII.—APppiicarions: 


(Ab) Anilin black. (Ox) Oxazin. 
(An) Anthraquinone. (Su) Sulfur. 


XXIV.—FINISHED PRODUCTS 
OTHER THAN DYES: 


(e) Explosives. 
(f) Flavors and perfumes. 


(AI) Azine, indulin. (Tr) Triphenylmethane. (m) Medicinals. 
(Az) Azo. (Xa) Xanthone. (p) Photo chemicals. 
(In) Indigo (pl) Plastics. 
(Nt) Nitro. (t) Tannins, synthetic. 
(Ni) Nitroso. 
COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
Abel, (yulitis 1.0 veg sare sos oe ne Gere eee Badische..... XV | 544,050; 679,199; Re. 11,973. 
and Fritz Kalkow ......... GeF. ca cae Badische..... XV esoeey 650,293; 658,055; 
’ 92,174. 
and Arthur Luttringhaus .. |Ger....... Badische. ..'.. XV_| 775,428; 777,323; 790,167. 
ACh RPItz sce ky a cease eis aie mete Ger. cores. Boehringer... | XVIIT| 707,813. 
See hoe 708,511. : 
1,053; (m)676 2 
Ach, Lorenz ........ccsesecess GEftone.s Boehringer... | XXII bey hie Ame Saree 
XXIV | (m}948,084. 
and ean Sutter ...... ae Pore: Boehringer... peak (m)922,995. 
Achtmeyer, TR URE: a5 pCOMMEr ESE ouee Ae OU sieice cl Pelee occ alee holece lake 1 1,429,265; 267. 
Acker, Edwin. See A. Zitscher. pl) 1142952655 #.aeaeaes 
F. Kunert and A. Winther. ; 
Ackermann, Fritz ............. Getieisess Berlin. sic4es VI | 1,173,077. 
(See H. Geldermann) 
and Ewald Steinback ...... Ger sccm Basie... hee. III | 1,437,783. 
Adams, Carleton C. See A. R. 
Grob. ’ 
Adams, Elliot’ 0.0) ..ss5 abe sence Galrtse css 
and (Hi: U, Haller asa eee Ohio }..6: U. S. Govt...| XIII | 1,374,871; 1,374,872. 
and Louis E. Wise ....... IN a] Aree U. S. Govt... }| XIII | 1,338,346; 1,338,340. 
Adams, Roger (see O. Kamm) . jIll........ 
and E. H. Volwiler ....... litt eee Abbott....... XXIV (m) 1,360,994; 1,440,652; 
1,476,934. 
Ahiam;- Chas..t.ceevicenaeteae Pata. u Pont. «<se5 XXII | 1,303,624. 
Ainsworth, William A. ........ Michsse ne Mather (1%). | XXIII} (Az) 1,310,518.- 
Aisen,; Maurice No 22. sno itll oe ties eulicciee eects XIII } 1,206,189. 
Akerbloni;  Ntist Lie eae ecir eee Sweden. heen saan ee XXII | 1,333,604. | 
Albert; FAugust ies o maces oe ote OL nn sickle ccs nc ete ee XXIV | (m) 1,425,920; 1,425,930; 
1,425,931. 
Albert-Jr* Talbots): +3 Dehieaeacs du Pont XXII | 1,393,597. 
Albrecht, "Karl icc cont coe Gers ce a alle . VII | 874,649. 
Aldrich, Thomas B. ........... Mich. se Parke, Davis. | XXII | 1,397,913; 1,451,357. 
Alioth, Manfred and Ernst ; 
Bodmer<. ; So oanuw estes sees Switz..... |Durand...... XIX | 1,403,888. 
Allegret, Augustin. See A. 
Blanchon. 
Alt, Hermann and Eduard Cul- 
Maly woe ete We malecvin dee se ts au6 Gera Kalle wii..simee XXIII | (Ni)615,232. 
Althausse, Maximilian C. L. ... |Ger....... Sthamer..... .| XXIII | 679,203; 679,204; 692,497; 
: : 692,775. 
Altschul, Julius .......-....5.. Geriossa6 Berliniwessese XXIV | (m)658,747; 1,183,711. 
See O. Mankiewicz) 
and Wilhelm Urban ...... Getincrea Berlin. co. ee V 1,183,711. 


yO ee 
ew vy 


Ls 
$i 


PATENTEE INDEX 530 


PATENTEE eh ee ASSIGNEE Jit PATENT NUMBERS 
PIEWEP PPT LECAM es fi. cia k cic deeioe oe 1 a doc er eae Soc Chimss.| All 115415,610: . 
Seed XXIV |(m) 1,414,333; 1,431,863. 
aneavid Ebin ...t..... Brevi ose Soc. Chim....| XXIV {(m) 1,375,949. 
and Joanny Landrivon ....|Fr........ Soc. Chim....}| XXII _ | 1,393,191. 
XXIV |(m)1,334,641; 1,334,642; 
1,418,900. 
Ambler, Joseph A. .......5... onilacetcrs : 
and Harry D. Gibbs ...... Galitieyee.s U.S. Govt...| XXII 1,292,950; 1,300,227; 
1,300,226; 1,390,241. 
SRA IDS ot eas cis 0's's itt oe es U. S. Govt...| XXII | 1,316,823. 
Amend, CVE crotelel tats e's. INN cc zene sree eee ences XXIII (Ab) 499,410. 
Ammelburg, Alfred .......... (Set eo ere Hochst. XXIT_ | 664,700. 
XXIV |(m)686,998; 686,999. 
Anderson, John. See F. W. 
Atack. 
Anderwert, Eugen (see B. 
NMNED PRN Gta gtae Saw tS liale-e'd ec « Sry itz acres 1,338,414. 
and Hermann Fritzche .... |Switz..... |Basle........ VI 1,233,742. 
and Heinrich Schobel .... |Switz..... |Basle........ VI 1,210,751; 1,265,030; 
and HH.) Pritzsche. ..:...... Rerite), ¢. oe 1 Dases ei ses os VI 1,265,031; 1,282,354; 
1,282,355; 1,282,356; 
1,292,385. 
Mmucreau, moland I. ......... Delite ci du Pont..... XXIV | (pl) 1,420,399. 
Andresen, Momme ............ Geri ns 6s Berltinn.<ticas XXIT | 405,938. 
Andrews, Chester E. .......... 1h eae Selden....... VI 1,314,921; 1,314,922; 
1,314,925; 1,314,926. 
XV_ |1,314,928; 1,314,920. 
XXII |1,314,920; 1,314,023; 
1,314,924, 1,314,927; 
1,324,715; 1,324,716; 
1,324,717; 1,336,182. 
XXIV | (m) 1,306,512. My 
marel Andres sa Ses... vga yak feoae dik he res Vv 1,340,696. 
Annaheim, Joseph ...... mr  (Switz....- |Duraad......- V_-|369,764. 
Mppelbaum Alan J; ....:...... Diese iets ovis Import By-...| XV_ |1,346,153; 1,346,154. 
XXII | 1,302,273. 
Armand, Nicolas C. .......... eee 
and Jacques E. Berton eee ne: | i ae XXITI | 242,855. 
Braet Rabert a... ..c. 5... Buctcnen ccs, he cheba oe VI_ | 1,395,238. 
FO aerae creel cieteneietere cneare VII | 1,414,164. 
Ashworth, Arthur ............ Pg ee ea esiaa ane Pes as a XXIII | (In) 437,638. 
and Joshua Birger ...... Eng...... [erersereseees VI 548,416. 
XI | 548,344; 548,345. 
XV __ |653,277; 653,278. 
XXIIT | (Ni) 548,346. 
Atack, Frederick W. ......... MRA Gleiafe Ness sine re siete nae XXII | 1,461,745. 
(see W. Haworth) 
and John Anderson ...... Scotec. ss: Brit. Aliz.... III 1,430,277. 
and George Robertson ........ SOO tection eich [necerexes sbatevets Greve XOX iG it40r, 125 
and Charles W. Soutar ....... COL ae cab listoeseke la eaters III 1,452,774. 
OMIT | 54525774: 
maspten, Peter -T. Suc si.c:.... N. Y.....|Matheson.....| XXI |491,972; 492,368; 542,403. 
pmouitervertec, sluttio .... | No Yo.... | osc ccne vceces XXIT |578,384. 
PEVOEY CC MGSICS El. as. snes esos Pare. See) leah a atk. ae XXI_ | 320,526. 
Bablich, Hermann. See M. 
Becke. 
Bachelut, Jacques. See J. 
Schmid. 
Backhaus, Arthur A. ........ 1 Cee U.S. Ind. Alc,| XXII .| 1,425,625; 1,425,626; 
1,437,483; 1,454,462; 
1,454,463. 
Baddiley, James, Joseph B. 
Byman i 
and Harry Wignall ...... Eng.e.ees British Dyes. | XXII | 1,441,655. 
and Ernst Bainbridge ....|Eng.....-. British Dyes. | XXII |1,452,481. 
(see H. Levinstein) 
Bader, Marcel and Charles Sun- 
MM ia ea Ske ano + Le Py een Durand (34). | XXIII |(1n)1,448,251. 
MER ONWidlteh) oc ssc cv ksc cscs Pug aves. Levinstein....| XXII_ | 1,396,913. 
~~ and Donald A. Nightingale |Md.......|...-eeeececes XXIII | 1,433,925. 
Beer LOUIS Gen es kek es cons Bngy: sss ; 
and Lionel B. Holliday ...jEng...... Hollidaysec. IX 1,349,802; 1,413,914. 


memeweianGes 166 Ee Silene canes NeeY en ie Bakelitemrr tr XXIV ’(pl) 1,088,677; 1,088,678. 


534 DIGEST OF PATENTS 
EEE yxy EI —————————{—{—_——=_=_ 
TENT COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE ceour PATENT NUMBERS 
Baever, 7. Adolt: jo ce. wiaeee a ee Gercc chs cep oe PED Ph VII |227,470; 228,300; 233,458; 
233,459; 233,460. 
Badische..... VII }235,193; 240,941; 250,035; 
250,036; 251,499; 251,500; 
251,501; 251,671; 259,260; 
259,261; 259,629. 
Badische..... XXIII | (In)235,488. 240,361. 
and Heinrich Caro ...... Geran ccs Badische..... VII |240,359. 
XXIII | (In) 240,360. 
and Viggo B. Drewson .../Ger....... Badische..... XVIII |257,812; 257,813; 257,814; 
257,815. 
and Adolf Emmerling ....|Ger.....-- Badische..... VII |240,942. 
Bailey, George C. (see J. M. 
ister: re 7 : Cc Peri oe a : eee wk Barrett.......- XXII 1,401,937. 
an ugustus Fever sat Ne die cest B eee ae 1,439,500. 
Bainbridge, Ernest B. See J. Leng ba Speco perfor 
Baker, Higdon M4. 
er, Hayden M. ........-. | ey PORTS Macy td IEE pes 
remta hs See A. Schmidt. K XI 348,816. 
Bally, Sal Ns oe ae paeeres Cee eee ee : 
vice H. Scholl and J. H. Cries Badische..... TIE |617,981; 618,000; 619,114; 
Bower) 619,115; 631,605; 632,621; 
640,986; 643,451; 648,331; 
648,332; 654,505; 654,506; 
656,081; 659,565; 659,566; 
666,594; 673,691; 688,576; 
79753735 79753745: 723,125; 
749,913; 753,657; 786,085; 
796,393; 818,336; 837,775; 
906,367; 1,016,604; 
1,026,621; 1,037,410; 
1,065,102; 1,077,115; 
1,086,123; 1,128,836; 
1,202,260. ot 
XI 524,235. 
XIX |617,627. 
XXII |631.606; 631,607; 631,608; 
759,751; 876,679. 
and Max H. Isler Ger : XXII | (An) 40,4109. 
ETERS ALR A aa sseee*+|Badische..... TIL = |809,892; 818,992; 820,379; 
and Richard Metzger ....|Ger....... Badische 1,093,427. 
eee III 6 
d Hugo Wolff .......... Ger SNe Weaedhieade dt 
meth chats 0: as RAGtaCaS <oxae IIt 793,558; 809,893; 809,894; 
811,471; 1,095,780; 
Barbet, “Pierre: Asi. t.3 nes core ty PERRIN rag Cte rps te 1,216,921. 
Bammann, Johann (see M. sees} XXIT | 1,459,081. 
Ulrich’) Wis ekeicccs are eurtoie cueteuotalet nas Gere cess Elberfeld..... e 
and Ernst Davidis ....... Gera lnavess Elberfeld..... Me res 606,264; 611,597. ! 
and W. <VoOrstetiis ccs «ces Getiiteves Elberfeld..... VI Pepin PD: : 
and Walter Vorster ...... Gee as Elberfeld,.... xxit |¢ :020; 650,621. # 
Barbezat, Charles «......00s00+ Switz..... Darand. 22532 XI 49,714. z 
Barbier, Andre (see J. Koetschet) 955,040. ; 
Barlow, George W. .......+-- NiO Pea ees X * 
Barnard, Arthtiti ence eee Delre eis icsts Gur Pont. 2... ee peer i 
Barrington, John ......++-+++- Mase: sos} eae eis XXII | eee iS 
Barstow, Edwin O. ....... +++|Mich...... Doe xxi |,’ au . ee 
Bauer, Hugo. See P. Ehrlich. »463,190. ‘ 
Bauer, Walter .....ceseeeeooes Ft oe Earl, § Raket tease mf 
Bauer, Wilhelm ......-++0+0+- Gare Beyer eee oe % 
VIE" lan eat : 
and Alfred: Herre ......« 99,152; 937,040; 1,466,687. 
Cet cnr s Bayer........ VII |937,041; 958,464; 958,455 
961,396; 961,397; 961,398; 
961,399 es otto) ae 
1,14797793 15434,903.- 
N. -Y...). «| Synthetic: 4.3 VII 11266062, may 
and R. Mayer ....--.++.- Ger. skin Bayefs.sieess VIL |985,767; 985,768; 985,769; 


985,770; 998,596; 

1,001,919; 1,005,140; 
1,005,141; 1,051,856; 
1,074,405; 1,101,778. 


PATENTEE INDEX 535 


—EEEES ee e=eee—_e=—Ee—=QqNnS=_ooeoe—eee lll I EE —e—eeEEeEae——S>—S>_—S>]_—S>]_aE>—Ee—__—>_——>—_—_———>—>>l>]ll>— oo —————_— 


PATENTEE pe yatiet ASSIGNEE | nous PATENT NUMBERS 
Pate EL CINTICH, Vs eek ccs ees Gers. csi is PIGChSty aa oe ste VI 210,233; Re. 9,986; Re. 
. 9,987; 233,465; 246,272; 
250,038; 251,162; 251,163; 
251,164. 
XXII 554,974. 
meee A IDETE. esas cats eyes des» Geri ie... Than. «0s XXIV | (£) 692,596. 
Bauschlicher, August ........ Aus.-Hng..| Roessler....., XXII | 608,019. 
Bayer, Friedrich (see C. 
UOT tg 0 SES ee eae ee Gervine «és Bayer ins: +33 VI 362,813; 363,502; 395,474. 
XXIII | (Az) 418,153. 
AZ LCT MP NEAK Wile lee uaisGis.e ess © Getsac esc Badische..... XXII 885,566. 
XXIII | (In) 657,307. 
and Theodor Wohlfahrt . |Ger....... Badische..... XXII | 793,559. 
Beach, Carl, Alvin Mittasch ...|Ger....... : 
and Carl Neresheimer ....|Ger....... Badische..... XXIT | 1,274,503. 
Ce ON Yvan se coechavavas 0s Getiis cnc: Hochsties .s.0. VI 844,845. 
XXIII | 1,002,118; 1,024,668. 
and Hermann Bablich ...|Ger....... Hochst....... XXIII | 666,256. 
and Albert Beil .......... eS aa Mochst,«.5 << VI__ | 623,697. 
” XXII | 995,431; (Su) 680,472. 
and Wilhelm Suida ..... Aus.-Hng..|Hochst....... III 1,196,422. 
Hecker; ‘Pranz %%sii.i.s.s... Aus.-Hng. |Badische..... XXII | 885,567. 
Becker, Theodor. See A. 
Eichengriin. 
Beckers, William .....0¢00+:. in ey ere 
and Issac Dreyfus ....... ty eee Beckers...... XXIII | (An) 1,228,089. 
Beckl, Walter. See M. Conrad. 
Bedtord, Charles S.-....5.055. Enrng.....2 |eceesceceeees VI 409,384. 
Bedford, Clayton W. .......... Ohior.. Goodyear.... | XXIV | (pl)1,418,772; 1,477,805. 
and Robert I. Sibley ... |Ohio..... Goodyear..... XXIV | (pl) 1,418,771. 
Behaghel, Wilhelm .......... Gerace as ‘ 
and Gustav K. Schumann .|Ger...... ,|Badische..... VIL |772:775; 818,341. 
XXIL | 778,772. 
BORTENE,  FORBRG oa ieee sss (CS Ce XXII | 667,358. 
Beil, Albert. See M. Becke. ; 
TT Be at 2 eae a ene Eng...... | cere ecereeees VII | 868,755. 
Benda, Louis (see P. Ehrlich) .|Ger....... Cassella...... I 1,427,431. 
XXIV | (m)1,408,974. 
Bender, Andrew J. ......... N. J... eee lereeeeesseeee XXIII | 1,301,360. 
enGet, Fritz oi is icc cee ees ein. Leonhardt.... I 503,305. 
VI 341,991; 344,075; 593,347>5 
606,436; 606,438; 606,439. 
VII | 662,754; 662,755; 690,346. 
XI | 494,838. 
XIV | 350,229; 350,230; 360,553; 
395,115; 396,527. 
XIX | 445,084- 
06,437. 
and Michael Kammerer ...|Ger....... Leonhardt... he 489,623. 
and Bertram Mayer ...... Gerires es Leonhardt. ...| ywyyy | 673,632. 
and Gustav Schultz ...... C3 See Leonhardt... VI 360,792. 
Benedetti, Carlo O. .......... De Vance ss 
; and A. P. and W. Vanse- NY , 
MW a wae Res ae f4 Aus e)WS wim oile,ece. 8 © 0.6 . et se Set ec 1 Ie OT RU I ee XTI 1,405,201. 
Berchelman, Wilhelm ......... Ger... ss: Elberfeld..... oH 764,837. 
Bayer aon 69167 ae Ill 958,850; 1,014,204; 
1,045,805. 
erences meRUOOlt 2.55 onex «ws 6 Geri ns eae: Elberfeld.....| xqIq | 752,323; 780,741. 
Weredpit, Alfred: (o. ceces s+ 0s Ger....00. Bayer.......- VI 912,356. 
Bergdolt, Wilhelm (see A. 
OE Gy CSS ae ae Ger....... Bayer....... -| VI |963,739; 974,346; 1,009,952; 
1,014,633; 1,052,647. 
Synthetic..... VI 1,201,544. 
Ber peliMeEClehe hs akic sc aus see Ger isnnone Wiilfing..... XXIV | (m)852,9903. 
Bergius, Friedrich. See K. H. 
Meyer. 
Berlinerblan, Joseph .......... Russia....|von Heyden..| XXIV | (f) 489,728. 
Bernhard, Eugen. See E. 
Zacharias. E 
Berns, Wilhelm .............. Geta ve Badische..... XXIII | (In) 690,347. 
Bernthsen, August ............ Gef....... Badische..... XVI_ | 282,836; 286,527. 
XXII | 282,835; 286,526. 
Bernthsen, Heinrich A. (see G. be 
PRMICEE See a a Sig's shad kb ¢ Geis sass. Badische..... XIX |516,584; 516,585; 645,781; 
646,794; 821,452. 
and George F. Jaubert ....|Fr........ Badische..... VIII | 617,628. 


Ger.......{|Badische..... XXII | 625,637. 


536 DIGEST OF PATENTS 


COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
and Paul Julias ..5..5.... Get vas ss Badische..... VI | 521,095; 521,096; 545,333; 
5551359; 558,344; 631,610; 
631,611; 644,240. 
Bertheim, Alfred. See P. 
Ehrlich. 
Berthold, sierich nti os Gera sat Berlin. o.3. vi 983,805. 
Berton, Jacques E. See N. C. 
Armand. 
Bertram, Wilhelm. See A. 
Schmidt. 
Bertschmann, Albert .......... SwitZ....< | Bases: tooo ee VI 724,078. 
XIII | 852,158. 
XV_ | 665,726. 
Bethmann, Fritz. See A. 
Schmidt. 
Bettey, Ralph. See J. Wolff. 
Beudet, Maurice. See J. 
Koetschet. 
Beyer ye Brune, «scr sie she shee enn Gerenr cers 
and F. Schaar-Rosenberg .|Eng...... Badische..... XV 654,087. 
Bibus, BertranG cee eee eee ee Aus.-Hng.. 
and Rudolf Scheuble ...... Aus.-Hng..]... Tee ee XXIV | (m)830,043. 
Bidaud, Florentin .0o....-...-- Pree Soc. Chim....| XXIV] (f) 1,418,904. 
Bielschowski, Oscar ......-... Ne eee ee XXIII} (Ab) 343,793. 
Bierer; oy OSephi ei. cect eee see Switzen 2 en|| Dirandenieere XI 534,809. 
XIX | 551,885. 
and Charles de la Harpe ..|Switz..... Durand...... XI | 531,148. 
Bigelow, Chas. A. See H. A. 
Wollenberg. 
Bindley, William T. See A. W. 
Weller. 
Bischler, Augustus ........... Switz..... |Basle.....3; VII | 727,270; 761,440; 776,884; 
839,099; 894,579. 
XIX | 759,657. 
XXII 78) 6p 86 
: XXIV 7,361. 
Bissell “Dos Wyse eee Ww Viewer Nati Lys Gs 
if (ste D. I. Cutrown) tional......] XVIII| 1,478,015. 
ackmore, Enry DS. .-.- eee, ING WX sin Siete dl ete seinen eee : 
Blanchon; ‘Andre’. $08 .525 3. Seb A Pik hes XXIV | (m)854,452; 889,171. 
and (AugustinJA egret 02.1 Bro uiacs 5 1o5 ot ee ee XXIII} (In) 522,042. 
Blangey, Louis (see P. Julius 
and A. Luttringhaus) ...... (Sete, coy Badische..... IX 1,166,808. 
and Carl Immerheiser ....|Ger....... Badische..... VI E,073,952- 
Blank, August (see K. 
Krekeler) cn¢a.5 tues see ses Cer ee Bayer........ VI_ | 1,023,120; 1,051,859; 
1,052,031. ; 
and Wilhelm Bergdolt ..../Ger....... Bayer. ..¢.55. VI | 971,111; 971,112; 1,082,923; 
1,087,429. 
and C. Heidenreich ;..... Gére hte re Bayer.......- VI 1,056,493. 
and “cm ansenian.ereteni tect Ger 5a. ee. Bayer..-s50i VI 1,082,581; 1,082,924; 
1,082,925; 1,087,430; 
1,090,379. 
Synthetic VI} 1,125,050; 1,150,656. 
and Karl Heusner ........ Gera Bayer; ¢« 2% VI_ | 969,450. 
A. Israel and M. Herzberg/Ger..... St Bavyetl.cs ae VI | 561,694; 561,709. 
and Matthias Latten ...... Gf. ideas Bayetiivcen et VI_ | 1,006,051; 1,087,427; 
1,087,428. : 
and Wladimir Rodinow ....|Ger....... Bayer... 4.0: XIV | 951,046; 951,047; 951,048; 
951,049. 
BianksRubin vc... eee Ger! ores: Cassella...... VII | 620,562; 620,563. 
Bloch; :Beniot 4.0 iaav ame Pee ee ee II | 79,942; Re. 3,103. 
Block J Davidse: a. eee ee Ieee Sunbeam..... XXIII} 1,361,811. 
Bloede, "Victor Gun uwet et eee Mdsees oy Bloede.,..... XXIII} (Ab)570,117; 588,387; 
588,388; (Az)593,192. 
Blom, Axel Vo oo vcak os ea ek Switein atl anaes XXII } 1,351,888. 
Blumenthal, Ferdinand. See O. 
Liebknecht. 
Blumfeldt, Alexander ........ Switza... Basle... ocee XXIV | (pl) 1,435,801. 
Bockmithl, Max and Gustav 
Ebert, 52. Seb acaeee cee Geren Hochst... shh XXIV | (im) 1,056,881. 
and Adolf Schwartz ...... Gere eo Hochet;, 2-5 XXIV | (m) 1,426,348. 
and Kurt Windisch ....... Grete <a Hochst...» +. XXIV | (m) 1,429,922. 
Bodmer, Ernst (see C. de la 
Harpe. and M. Alioth) ...... Switzeewen Durand...... XIX ! 1,106,185. 


PATENTEE INDEX S37 


COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GRour PATENT NUMBERS 
mocdeker, -Fermann ....6..... Getinc cons HiGchst.. vex XIX | 438,053; 493,241; 615,791; 
641,184; 649,716. 
and Carl Hofimann ....... cr eee Hochst.o..3'.5 XIX | 642,893. 
BOchlccu martin fics wie si,s0 + Gero niece Cassella...... XXIII} (Su) 625,717. 
OHING MEAOOLIe Ee cc. cess sas (Oe ho Sood be bea ico Giomore XXI_ | 329,125. 
Bohringer, Alexander ........ ee Se crt baie ee es XXIV | (m) 282,488. 
monirer, (Melchior: ... 02.5. .00.. Switz....+ Sandozsae. ster VI |584,981; 591,616; 601,033; 
608,024; 640,989; 841,371; 
901,675; 959,109; 
1,014,039; 1,014,114; 
: 1,199,233; 1,199,234. 
aad) lan wagutt: oo... ee SS WitZ, os 2% Sa nlogoesa we VI_ | 627,679; 652,456. 
Boessneck, Paul ...........+-- PCL ane a'e i] uealeneras caine XXII | 715,748. 
MOtHUGET EAU! enc ew ee we MiursSia oo. |. BeTiin gh ess VI~ 136s, 666: 365,667. 
mrawert Marston TL. 5.665. s ss Woe. s a eke ao Ves t.022,055; 
Bohn, René (see P. Jeanmaire)|Ger....... Badische..... TI | 681,613. 
III | 348,613; 368,054; 399,479; 
399,480; 399,481; 399,482; 
401,633; 401,635; 415,088; 
452,210; 502,603; 519,229; 
609,327; 623,069; 627,896; 
631,613; 631,614; 633,950; 
646,795; 646,796; 647,370; 
669,894; 682,523; 692,762; 
724,789; 739,145; 739,579; 
753,659; 756,571; 767,259; 
787,824; 791,869; 806,053; 
844,914; 868,399; 948,204; 
970,878; 1,280,648. 
VI | 401,634. 
XI | 440,536. 
XV $45,3365 $45,3373 540,5705, 
32,170; 1,436; 79400. 
XVIIT | 484,697. 
XIX | 623,069. 
XXITI} (An)379,150; 746,784; 
1,055,701. 
and Carl Immerheiser ..... Geta. .... Badische..... III | 1,090,123. 
and Paul Nawiasky ...... eves. aes Badische..... VI_ | 1,264,604. 
Bolton, Mimer* Ko i... ).......- De Ee. du Pont... XXIT | 1,320,443. 
Poles Charlee (O, oie ens ene Ss anol al ad Wel eat dee Rg XXI_ | 1,321,973. 
Bonati, Anton ...........000- es Gee Rallies... XV_ | 695,533; 605,534. 
Boner, Johann H. ............ rere. ae. Badische..... IIT | 885,577. 
and Heinrich and Oscar XXIT | 1,083,051. 
TAU? eon ae ee re avs Ne ee Badische..... III | 1,026,557. 
Bonhote, Gerald. See G. de 
Montmollin. ~ 
BODE POUBINER Coos. oicw ewan es NOUS Coes elk net aren ee mM | Oa0.251; 
OTGlN, SPeDCeE® 6. 2s eee eos EE pe Bis ie ek EE eta eee XXI_ | 109,489. 
IS ORS Anti OEOd ac cc ois eie ele Gerigocss Benlitern. sa VI 1|454,840; 468,539. 
POMONA AT! Wore che hoie)ss < o.00' 6% « Geri css Badische..... XXII | 1,173,550. 
(see K. Neresheimer) Chem. Found.| XXII | 1,344,673; 1,369,383. 
and Wilhelm Meiser ...... Geis nic: Badische....- MOXY |1,420,403- 
Bstiecatt..t Gmond.. f.s..ces <0. Gepen cies AMET Gina OAS XXIII] (Su) 747,295. 
Bourcart, Emmanuel ......... Picea s Com, Paris...| VIE | 1,293,680 
XVIII | 615,472. 
Bouvier, Maurice ............ Bree soos Soc. Chim....}] VII | 1,412,038; 1,414,335. 
(In) 301,475. 
Bracewell, John ..........+...- hacer ts | waite Oeteeie.s as XXIII| (Ab) 400,819; 409,820; 
409,821; 409,822; 409,823; 
500,558; 
GAOT EGON Vay kw cicire cen ees Switz..... |Durand...... XI | 497,114. 
rack ei onant fo) oes ose ees Switz..... Durand a... VI |515,807; 516,468; 516,756; 
516,757; 516,758; 516,759; 
516,760; 519,522; 519,523; 
531,149; 542,073. 
Basle. cect XIX |613,113; 625,536; 643,371; 
695,441. 
Durande...-- XXII | 516,752; 516,753; 516,754; 
516,755. 
Bradshaw, George B. ........- Conn... [dees oe cate sas XXIV | (e) 1,398,098. 
Braren, Wilhelm. See < 
Luttringhaus. 
Przach, RicHATG i660. 2 eens Gera... Hochst....... III |5609,404; 569,405. 
Shia; dstShsboGle ae op acoeme Geeriiee axe Berlinvyerern's ae XXIV | (m) 659,204. 
Bratkowski, Wladislaus ....... eRe ae ion ok Uibestaratanshe ietersians' XXIII] 1,002,635. 
eG INTIS ek ois ee eee ees Gerace te. Elberfeld..... XXIV | (m)621,319. 


Pret. OTtO sn cs ses cee Bieter ars COR Sue vib nl os baad WIA VI | 289,613. 


538 DIGEST OF PATENTS 


COUNTRY DYE 

PATENTEE OR STATE ASSIGNEE GROUP 
Brenzingerswwarl poste ce ens Gere ee Bayersioneo VI 

Breuninger, Friedrich ......... Geri. sis os | Cassella...an. XXIII 
Brewster, Theodore J. ........ Naty cccnull wists aot aiadeee ts IX 

XXIV 

Briegs, <7 on! Beis sik wees ate sree Hing.<ssis Amer. Cell... | XXIII 

Brink, Francis N. See lL. A 

Pratt. 

Brochet; “Andre. ij.cs ce etk a tees Pts. cegeawte se Shae lara whale XXIII 
Brock, Frank P. See LL. V 

Redman. 

Broemme, Edward .........-+- Russia....|Deneys (%4). | XXIII 
IB ronter ih UIsUSin tele ota hes sae Geri coe serena tereteeaie eis XXIII 
and Hermann Gutzkow «...|/Ger.... 000] seceecesceuys III 
Broniatowski, Heinrich ....... SWiEZ. 2 aie walaSle nts es ewe Ill 

Brooke, Arthur. See R. 
Simpson. 
Brooks, Benjamin T. .......s.- Pals du) Pont? co... XXII 
Chadeloid....}| XXII 
Brown, Oliver W. .«..-.ecees- Tndse 
and Clyde O. Henke ...... i Gate Wen eee ee PARE rca XXII 
Brown, Ralph L. See F. W. 
Sperr, Jr. 
Brown, Wade H. See W. A. 

Jacobs. 
Browning, William .......... Engsiwe ys Arnold. .cy Ace XXIII 
Bruck, Walter. See W. 

Herzberg. 
Briinner, Walter. See J. 

Schmidlin. — 

Brunck, Heinrich ........-+.- Getines ane Badische..... III 
XXIII 
Brunner, Arnold ......-eee+> SOF gens 3 Hochst. .5 0s XIX 
(see K. Schirmacher) 
Bryk, Ernst (see A. Schmidt) ./Ger....... Hsochetec. ase VII 
Bucherer, Hans T. .....s+.-- Get euss + Kalle, js uses VI 
(see C. Schraube) XXII 
Buchner, Max. .sscccescesens Géfiun as nk Boehringer...| XXII 
XXIII 
Bilow, -Catl esas woneenach ee rere ted sn Badische..... VI 
Birger, Joshua. See “A 

Ashworth. 

Bulk Mises iy canes nie Stem a Ger....... Bayer, 5.5). TI 
(see J. Flachslaender and 

K. P. Gralert) ' 

and Alfred Thauss ...... Ger....... Synthetic..... XV 
Bull, Henry and Carl UL. 

Maller ype, vs os Cheb eet Ger....... Badische..... XVIII 
Bundaman, Emile T. ..,-.2.°: Calif...... Point Loma..| XV 
Burckhardt, Rudolf (see C. de , 

ja Harpe} sic eannw ee ceee Switz...» |Durand..o.4 Vv 
Burdick, Alfred. 8. y.- 005% 4s FN PR eet 

and Elmer B. Vitet ....:. Tian: Abbott....... XXIV 
Burghart, Lloyd Me j.sse<sess Md......% U. S. Ind. Ale | XXII 
Burrage, Albert C. Jr. ....... Mass...... ; 

and Guido Meisel ......... Mass...... Atlantic...... XXIII 
Bye, Mottimery xcs sGoauea sees Mich...... 

and Lewis H. Carlson ....|Mich...... Stearns...+2. XXIV 
Caberti, Luigi. See E. Lauber. 

Cabiatie vy imitans oc aawie slere crete Ltaly aviesc lksievia tena stot XXIII 
Cabot.. Samael Sire i. cen ee er Massie iinl cictw siete telerereins XXII 
Callseny SJ argen Sl asisien nolo ae Ger isasiees Baverin eacies XX1V 
Calvert, Jackson. See D. B. 

MacDonald. 
Camus, Edmond, Rene Duche- 

min 

and Gaston Criqueboeuf ..|Fr........ 6 apts acaasalalern XXII 
Canter, Vernon C. See C. L,. 

Voress. : 
Cantor. Max tio ie sale ee es ele sees GRP lene we Berlia idence VI 
Carlson, Lewis H. See M. Bye. 

Caro, Heinrich (see A. Baeyer)! Get. .5...651 «sess s sneha III 
Badische....- VI 

IX 

XVI 

XVIII 

XIX 


PATENT NUMBERS 


993,020. 
(Su) 660,069. 
1,380,186. 
(e) 1,380,185. 
1,425,364. 


(In) 1,247,927. 


560,890. 

(An) 275,128. 
97,597; Re. 4,558. 
968,533. 


1,324,143. 
1,394,664. 
1,451,489; 1,456,969. 


(Ab) 491,673. 


258,530. 
(An) 258,531; 274,081. 
990,224. 


877,702. 

1,024,308; 1,026,902. 

1,022,019. 

700,670. 

700,671; 700,672; 736,204; 
736,205; 736,206. 

524,665; 590,088. 


998,156. 


1,175,230. 


346,022. 
897,873; 909,277. 


1,174,820. 


(m) 1,436,304. 
1,426,457. 


(Su) 1,383,071, 1,383,072. 
(m) 1,439,605. 


(In) 559,163. 
184,142. 
(m) 1,424,236. 


1,297,792. 


1,042,198. 


186,032. 

204,799; Re. 9,144. 
225,108. 

204,796. 

204,797; 204,798; 250,201. 
625,641. 


. 
a ee 


PATENTEE INDEX 


COUNTRY DY 
PATENTEE an aan ASSIGNEE | our 
Siti ALeTeU INEIN vues cess SWwitZesst ni oadische ag a. IV 
XVIII 
and C. Graebe and C. Lie- 

METMANMerereiee st «Cleese 6 3 Gleties cx eal tas cee aree ke bee III 
eATOe me NSOCEM © cin stole ev s.00 0% Gertie) se. Cianamid VII 
Rraretens, FORA c.icescceces Ger sslees BVET rs lec. XXIIT 
Gatecm olanG im Cn catesiasaes 2% > Lar rerie a's Sunbeam..... XXIII 
Ceresole, Maurice ........000. Geri cue: Badische..... XIX 
Chapin, Edward S. .......... MIARE oe och care Cree ae eink XV 

ANCE TI GeSSED (ips cas Mass...... Amer. Dye VI 
Chatheld,. Clas. Bo ....5.0... We daciee latvia Pleteeatens (Ss XXIII 
ee euiiGt, PLGUTA cick svc eshcces BENG eae: « fhm eat a hiets s XXIII 
Chebotaref, Leo F. .......0.. N. OY. National..... XXII 
Cheever, Joseph C. F. ........ Wee ce ei al tase heme eas eal XXII 
Chevalier, Philibert .......... Lg CORR ees (Cr rrr XVIII 
Christiansen, Jens Anton ..... SREP ee aaa? | ig os dee Se XXII 
Rte LMU OW TAN 6 oc es nee 65% RR dit Peer eenies + os XXII 
Rei. an bert t1,. osc s bes ees Mass...... Metalite...... XXI 
Relar ke MELOne (las sce cose hos N.Y: Eastman..... XXIV 

and William W. Hartman|N. Y. ...]|Eastman..... XXII 
Classen, Alexander .......... Eig Rag ray Elche gs Lee ght XXIV 
nue, meer H., Alfred Ree 

tee ae CUle weld 6.5 UE o's 1s caacese cess XV 
ee Albert, Bernhard 

Schoner and Otto Siebert ...|Ger....... Berliners cr VI 
Breet OP EICUTICH (occ cis ca cece’ Chey Rar teeal Keiie oMIaa e XXIII 
Clemm, August. See C. Clemm. 

REMOTATD; COMMS -. 5 5 os Coa ou we see oe B.ceseene 

and August Clemm ...... NPOR ee cig | ew eGee es inns XVIII 
Clingestein, Heinrich ......... POR Payeriies. sa VI 
Clover, Alphonso M. ......... Pama. eal oe so hee es XXIV 

Parke-Davis.. | XXIV 
Cobellis, Fabricius ............ rere ite sl Suiire coos eaak XXII 
Srobenzi, | Alpert... vse acces eae oo ae Hochet. ic. hg - 
SO PIETCS VEFeil ois cs san cese Nek 

and Harold W. Walker ...|N. Y. .../Com. Res XXIII 
Coen Jr, W.. Wesley .......; POU ote 1a aleve ee ae | 
BOUe, SC AREONCEs De nd once eke Pace aa etoe ctw aie piccem! ov XX 
ME RODESE RM ss nce ace ke « Chia. cx: Collins (1%) XXII 

BTR pores Sp XXIII 
Colman, James. See R 

Wolffenstein 
Conant, George A. .......... INVASS Feretiets | secraetnatedang eee XX 
Cone, Lee CTE oes din aa MTC Waar: Dowie cs VII 
Conklin, Theodore F. ........ WD leeerees tir al erstere ta crate wictetsse xX 
Conover, Courtney .......... fot Ba te ae Selden....... XXII 

and Harry D. Gibbs ..... ROaTGE ate 54 U. S. Govt XXII 
DORUG MON ee oe oy a sn os Co ee Héchst....... XXIII 
and Walter Beckh ........ ReOR ek Pe oaidcae re ace ase XXII 
memererry ATOM yd. ocacsc une . Switz : Geigy te olannis XVIII 

poke diesty J: .......2.... N. Klipstein (14)| XXIII 
Roombs, Frank By. si........ Cetitere et ln reece ek 
Cooper, Herman C. See R. H. 

McKee. 

Copthorne, Howard N. ....... Ly Resear 

and A. Te -Tannehill ..... DnB pee yaic:\tercatetets cites <x XXIV 
Corell, Martin. See G. 

Kranzlein. 

Cornelison, Robert W. ...... Pe cannes 

and William H. Warren ats N. Y es ee ee ee XXII 
Cottringer, Paul .............. Mich,..... Dow......--- XXII 
Craver, Augustus E. .......... Nos. Barrett. 2355: XVIII 

(see G. C. Bailey) 

Cresson, Benjamin Ny tit, See PPA dea ate as nce we cee alana aye XXIII 
Criqueboeuf, Gaston. See E. 

Camus. 

SRCROIY, THOMSS 6655205 a0 000s Conn.. Amer. Cloth..| XXIII 
Culmann, Edward (see H. Alt) af Y. ....|Schoellkopf...} XV 
Duleser, Harry He vie wss sce: NV areraterete tae |iave cree eee eens otetors | XXL 


35 


939 


PATENT NUMBERS 


301,802. 

290,856; 308,748. 
153,536. 

860,900. 

(An) 1,126,387. 


1,307,113; 1,349,265. 

377,349; 377:350; 449,520; 
456,081; 516,588; 516,589. 

909,151; 909,152; 909,153; 
909,154; 909,155; 909,156. 

1,106,781. 

1,429,714. 

(In)885,978. 

1,381,280. 

131,393. 

53,241. 

1,302,011. 

648,380. 

1,367,862. 

(p) 1,434,429. 

1,411,683. 

(m)618,167; 618,168. 


639,806. 


1,213,075. 
(Ab) 727,292. 


50,335. 
1,076,819. 
(m) 768,562. 
(m) 1,286,944. 
1,30 1,909. 
578,093; 
454,535. 


588,397. 


1,332,028, 
1,243,042. 
1,361,139. 
1,445,870. 
1,396,320. 


302,544. 
1,211,413; Re. 
1,419,720. 

399,974. 
1,324,443; Re. 
1,417,367. 

1,285,117; 1,301,388; 
1,303,168. 

(AI) 328,465. 

811,826; 811,827; 811,828; 
811,829. 

877,052; 877,053; 877,054. 

(Su) 769,059. 


14,364; 


15,520; 


1,327,862. 

(pl) 1,353,220. 
574,395; 574,396. 
1,466,991. 

1,470,554; 1,470,555. 
(Ab) 390,842. 

46,200. 


711,038; 731,669; 746,926. 
1,409,083. 
(pl) 1,430,538. 


540 


DIGEST OF PATENTS 


| COUNTRY 
PATENTES | OR STATE ASSIGNEE 
Curme. Georser Os .-aee cena Bareecnyre 
and Herman 6. Hayn’-<:. =|Pa...a. os Union Carb.. 
Curtis, “Harry <A. See W. 
Runge. 
Cutrona, Dominic J., ......+-- Neuve an 
Robert B. McCann 
and Don W. Bissell ..... N. Y. National..... 
Dachert, Alfred .......--+---- Ger oe 
and Charles Heitz ......- Ger iii7. a be aeak biter aes 
Dandlicher, Gottlieb ........- Gera 
and H. A. Bernthsen ...... Geeks Badische..... 
Daimler, Carl F. See M. 
Hoffman, 
Dale, John G. See N. Lloyd. 
Daniels, Lloyd C. ..-++-+-++s- Naktis National..... 
and Winthrop S. Lawrence|N, Y..... |National..... 
Darier, George ee Paul 
Julius and H. Terrisse. 
Darrin, Mare (see F. W. 
Snerr) > ate ss ase ech mee sie Pare isa Koppers..... 
Datta, Rasik Lal ........+---- [belch ye RM RAL SR cincrapsie 
and P. S. Varma .......-. Trdiat Geen nbe eto miciaee 
Davidis, Ernst. See J. 

Bammann. 

Davies, Arthur H. ........--+-- En pee Scot. Dyes... 
Davis, Alex Bo. 2s <\se.ce sees Ind Lilly c.f eens 
Davis, Frederick .........--- Hingis set Baversnasnees 
Davis, Tenney L. .......----. Mass......|]-eceeeececees 
de Grousseau, Edouard ....... Peetu 

and Auguste Vicongne ....|Fr........]--+-- We routes 
de Haen, Cath JilEw anes. 1 oe Gertie ec ccc cc cceces 
de la Harpe, Charles (see J. 

Bierer, C. Oswald and C. A. 

MMAVET) a 56 Gk ks gear ie emt SwitZiceen Durand... 
and Rudolph Burckhardt ..|Switz..... Durand...... 
and Charles Vaucher ..... Switziy oc. Durand.....- 

andwiies woretanecmate ies Switzer Diurand.sae 
and Ernst Bodmer ...... Switz..... | Durand... . 
and B.Zehntner’.......°. Switz.; <2 Durand... %< 
and pike Oswald a tiers cee Switz Durands.. sc 
Ges Lalande belie. esto. sae Bos touch tok gee 
de Montmollin, Guillaume ..... Switz Baste. 5.4.05 
and Gerald Bonhote ..... Switz Baslestacke 
and Heinrich J. Spieler ..|Switz Baslershacscr 
and Josef Spieler ....... Switz Baslesecanntis 
Dean, Harry. Sée J. Turner. 
Dedicherny Fens i258 sos Os Geti<t- aes Berlin....... 
(see R. Kirchhoff) 
and Werner Lange ...... Ger Pete Berlin: 2.56 
Behn, William’ M.eso59.5. 55s Widahh. nti canna ou cree 
Dehoft; sWenpold i.e cutee ROT sae des 
and G. Wessbecher ......~ Gere en Badische..... 
Deicke, Bernhard ............ Geri wale Hochst.scus 
(see K. Schirmacher) 
Deinet) Joseph Laer ee er ae ere Bayefis 4. 0oe% 
Delaire, George E. C. ........ BMGs wltaise’ | arsine mee eee 
Demuth Roberts once tees Gere ue. os Bavyenovn etic 
Elberfeld.... 


DYE 
GROUP PATENT NUMBERS 
XXII | 1,463,255. 
XXII | 1,434,593. 


XXIII} 1,172,113. 


XVI | 416,055. 


IIT 1,464,598. 
1,365,024. 
III | 1,478,027. 


(pl) 1,236,917; 1,297,328. 
1,326,579. 

1,350,092. 

(e) 1,292,266. 


III eee 
m) 1,138,936. 
XXIIT}(An)0984,545. 
1,417,369. 
XXIV | (e) 1,417,368. 


1,386,166. 
XXIII 482,477. 


XI |585,034; 616,622; 663,220; 
663,221; 704,301; 707,832; 
707,833; 863,907; 897,619. 

XI |842,303; 898,040; 898,842; 

XI {6 eae 666; 638,576 
13,578; 629,666; 638,576. 

XI 1662,224. Ses 


XIX |1,002,825; 1,003,257. 
1,055,864; 1,055,885. 
XI | 808,030. : 
XI }898,098; 1,055,864; 
1,055,885. 
we 188,061. 
, 1,359,969; 1,467,711. 
XXIT 1,467,712. 
mo 1,387,596. 
1,453,660. 
XVIII 1,460,315. 

XXII |1,453,6590; 1,474,928. 
VI {717,550; 1,319,852; 
1,416,621. 
VI_{1,180,985,; 1,183,831. 
XXII | 1,460,708; 1,472,791. 


XXIII | (Az) 778,175. 
VI |610,345- fs 


{Tl |874,473; 874,474; 803,837; 
935,590; 935,781; 938,618; 
938,619; 957,039; 957,040; 
957;041; 957,042; »146. 
XXIII} (An)972,066; meyer! : 
978,139. 
XVIII | 32,965. 
603,755. 
606,193; 611,610; 611,611; 
614,538; 620,428; 656,631; 
673,388. 


PATENTEE INDEX 541 
COUNTRY YE 
PATENTEE Nien ane ASSIGNEE | group PATENT NUMBERS 
OO tC ee tba) a detapean a dl Sele Ream Sa arcemere XXII | 1,228,414. 
XXIII} 1,320,454; 1,322,203. 
Dennison Charles) H. 25... Miasswycces Amer. Rubber | XX 1,332,974. 
BIEL EE GA) Farias oc Ging si ds'es 5 os Tndkeie = 
ance William: Huigbure) .... |Inds.... +.» Retliviers eiciecars XXII | 1,445,668. 
Derick, Clarence G., W. M 
Ralpnana UL. W.-Flett)..... |N. Y.. National..... XXII | 1,394,150. 
PPOCRTIATi sO IO MEEL ces cca so 6 100s etic nes« Bay etc as VI 1,051,565; 1,059,599; 
Synthetics... a -oV-L 1,125,073; 1,125,074; 
1,126,413. 
and Arthur Part ..c00.- OPS ee Bayete. ccs VI 1,052,136; 1,052,137; 
1,058,562; 1,058,692. 
and O. Gunther, H. 
Schweitzer and A. Zart .|Ger....... Bayer oases VI 1,052,135. 
Descamps, Louis ........:.- Le — ee (ence yen pr ient lea XXII | 769,593. 
Riatioss, . patrick ois in «<n. igh eee ee Baier a ek. XX | 804,798. 
Dick, James. See F. W. 
Skirrow. 
Dieffenbach, Otto .......c0055. UE des nek Ee sete cece anes XXII | 833,513. 
VACA og AS a a Get cc. te LAUREL cs sa VI_ | 380,098; 401,483. 
Berliners cc VI 491,410; 512,167. 
and Max Moeller ........ Cet ess Berlingo eu. ss VI 511,688. 
Dieterle, Paul. See R. Gley. 
Dieterle, Wilhelm ............ Cfo veuck Haut... .. ..-| XXIT | 602,682. 
Ditke james H....2s0cs eens N. Y..... {Raynolds..... XX | 72,817; 72,818. 
Dissosway, Thurston N. ....... INI W ceca Dissosway....| XXII | 1,446,550; 1,446,551. 
Divine, Robert B. .........5.. J) ee ise sea wowene XXII | 1,301,662; 1,301,663. 
Twitchell.... | XXII | 1,303,779; 1,330,624. 
Doebner, Oscar G. ........-. orks OC Laee es owas XVIII} 222,257, 
and Wilhelm von Miiller ..|Ger.......[--++ceseeeees XXIT_| 300,035; 316,248; 316,249. 
BGC UMtAW Can cee eel sass gene ea ihe mane XXII] 1,047,923. 
DIGIUM OROS Cy can aks wees ses Ger. Chem. Fab... | XXIV | (m) 1,045,377; 1,045,378; 
1,045,379; 1,197,462. 
OGUTES EAE oe simp eeise nos To Re Theat sl. XV_ | 710,766. 
and Rudolf Hagenbach (erm. Hochst)... %.. XIT_| 731,670. 
Motald; Georve ecusiacie pes es Mass... 2: ‘Arnoldigeases XXII) (Ab) 491,961. 
Donahue, John a Aes cae N. f Bastman..... XXIII} 1,415,023. 
Wonvan, Robert M. (oc... cee @retas ose cae, A ae XXIIT] 444,220. 
Donovan, William T. See Robt. 
G. Griswold. 
Dorrer, August. See E. 
Schleicher. 
Downs, Charles R. (see J. M. 
AVM tee soi kas kee ud eee Barrett....... XXII | 1,290,124; 1,301,785; 
1,303,639; 1,321,994; 
1,374,721; 1,374,722; 
1,464,844. 
and Ralph S. Potter ...... et ae Barrett... 3. XXIT_| 1,364,547. 
LE dhe hot 02 ee a AL Shae ee Boehringer...| XXIII] 597,401; 630,199. 
Drescher, Bruno. See D. 
Vorlander. 
PIP OGNG ERAS dss ces kaciss>s>|(Cer.....s- 
(see B. Heymann, A. Israel 
and R. Kothe) 
and DMMyrtil Rahn ......./ Vio Dn eae Pavers awe VI_ | 843,077. 
and Richard Kothe ....... ariet. Bayete cee: VI | 858,444; 859,930. 
and H. Hoerlein ....... [ed ee Bayers.c. eae vI outer 978,438; 978,439; 
959,954. 
aid AS Duss... ees oy Bayerse; <asu VI_ | 980,953. 
and Anton Ossenbeck ....|/Ger....... Bavercn 2.2 o. VI | 843,137. 
Drewson, Viggo B. See A. 
Baeyer. 
MOPEV6OS)) CRANES oy si) cca eee oe Eng...... Clayton. sic\<1s VI_ | 441,945. 
Breit se PICT Vi cy obs aisle me ns TS ACI Sean es XXII | 1,338,979; 1,368,789; 
1,430,304. 
Dreyfus, Isaac. See W. 
Beckers. 
Dubois, Alexandre N. ........ | Fe PAC LSE, ete Peas XXIII} (Ab) 283,220; 287,112; 
331,777. 
Duchemin, Rene. See E. 
Camus. 
Diirkopf, Ernst H. C. ........ Gert na Merekon.. 5... XXIV | (m)598,914; 601,072. 
Duisberg, Carl ............... Geen Po aes teenie ae VI_ | 329,632; 329,633; 342,432; 
357,273; 357,274; 388,185. 
Bayer...... ‘ VI_ | 366,078; 394,841; 423,550; 


432,989; 447,302; 447,303; 
467,162; 476,371; 481,934; 
499,216; 525,492. 


542 DIGEST OF PATENTS 
———yyIIyIIIlIyICylIEIIyIyIIyEESEE eS eae eeaaaee aaa 
COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
Duisberg, Walther. 
See R. Willstatter. 
Dunning, Wilbur G 
See W. B. Murphy. 
Dunscomb, Daniel ........-..- Tg gee ates HR ed a SEE RL XX 259,832. 
Durrans, Thomas H. ......... Png. i} Poakess soe. XXII | 1:326,040. 
Dziewonski, Karol ...........- Poland. ui: cates s XV 1,471,150. 
Sp athe hy See P. Reid. . 
belizig,; F2a06 ss occ cee ce heal Ger Ratlesie oe XV_ | 723,448. 
Ebert, Gustav (thi scess hes eb el itee)) Ln Hache oc (m) 464,861. 
Phin David.ic See TC Altwegenl Con ee aa sre 
Eckhard, Fritz. See R. Just. as 
Eckmatin, Aron <554 6606s 0 -la10.6 itz..... Schweiz Ser.. Mm) 1,347,083. 
Ehrhardt, AG F. and oie i hiAin Misia bas! 
Herbert! Wi ices 4 omens 6 aaet Ring! oe ute eee ee 1,281,243. 
Ehrlich, }Panl- 50 ay ip Mua 
and Hugo Bauer .......... Gerkesic: Hichsti ce XXIV | (m) 1,087,157. 
and Louis Benda ........ Gere. 5G ue Cassella...... I 1,005,176. 
and Alfred Bertheim ..... Gere oi dos Hochst....... XXIV | (m) 1,059,983. 
_ and Paul Karrer ......... Cer) ict tt Hichst.....-. XXIV | (m)1,120,700. 
Eichengriin, Arthur .......... elise hb tho bankas XXIV {m1} 567,068, 
Bayer. d.5 es XXII 755415. 
of yet are Becker ..... Gere ks Elberfela XXIII Apapersa 
ichhart, Sylvain .. shaven saes Rp an _ Chim. I 772,560. 
Spat Heinrich (see O. ; me na Ms i 
POSEY vie are victels atanre et etetncels ate Gag cis etree he VI 1,123,263; 1,188,421. 
Eiffaender, Ludwig. See A Lal Hochat : a x 
Luttringhaus. 
Einhorn, Alfred ...-......-+-- Gere Hochst....... XXIV | (m)610,348; 619,540; 
624,772; 625,158; 625,159; 
812,554. 
Eelbel,y Mark. (1's. 2.40 tee visa oe Ct Kalter ste VI | 778,476; 807,422; 958,912; 
1,023,199; 1,028,006. 
VII | 965,170. 
XII | 1,026,257. 
XV_ | 778,478. 
; XXII | 778,477. 
and Julius Oppermann ....|/Ger....... Rallies: cease VI_ | 620,574. 
and Ignaz Rosenberg ..... eras cits Kallas eo VI_ | 613,638; 613,639; 613,640; 
671,543. 
4 Edward W A aS 661,907; 667,689. 
an war ray Can ee Oven, oe CD is) cielo: eta K ll coeeeoeee > . 
Elbert, Gustav. See M. ie eaieh: 
Bockmuhl. 
Rilis, Carleton s,s sore vee ges NS poe wires Ellis-Foster XV _ | 1,187,614; 1,274,351} 
1,279,307. 
XXII | 1,306,221. ~ 
Ha ee Sais 1,365,046. 
and Alfred A. Wells ...... re ed pars PANN aici 
Bisaesser, \Emilsys seiana a ses oe Getiaccces Dablocst ee Vv 392,723; 524,677. 
ap « hoal d wise tabernae VI_ | 320,634. 
oer A ees bee Me 611,111. 
ah eatee aatee 548,158. 
Dahle axa os XV 611,112. 
Me Muiaviakatere panes 607,408. 
Elvert, ‘Heinrich. 645 000 7 104" Ba Sole an ee ee 
See K. Schirmacher. 
Emilewicz, R. See M. Lange 
Emmerich, Wilhelm .......... GEP.5 ain os Hochst....... XV_ | 760,110. 
XI ,006,738. 
Emmerling, Adolf. See A. A | Cees 
Baeyer. ; 
Endemann, Hermann ........ AE GEA Pape h Ss ug ert XXII | 277,864. 
(see W. Pickhardt) aa 
Benga, Carl )0 i. da enenar bees Ger. Casactiay sek XXIII] (Az)711,953. 
Hugi, Gadient’ o.oo vcrcnb ves Switz..... |Basle........ VII | 831,844; 836,309; 841,003; 
848,354; 848,355; 848,356; 
856,687; 856,776; 867,714; 
867,715; 872,115; 872,227; 
872,280; 876,158; 883,703; 
887,609; 888,230; 915,338; 
923,959; 954,273; 
1,043,682; 1,074,850. 
XI | 1,199,458. 
XXIII} (In) 893,468. 


Tee eR Eee ee ne ee 


— 


PATENTEE INDEX 


543 


—eeeeeeeeeaaayayyyEyeeeeeeeeeeauauauauaoeaoooooeooaoaoaoaoaoeeeey~eaeaeEeeEey————————————E———EeEeEeEeEeEeeEeEeE—e———————————SS 


PATENT NUMBERS 


PATENTER omstare | 8910NxR | croup 
and Jarosiay Frohlich ....)/Switz.....]Basle........ VII 
XXIII 
and Fritz Grieshaber ......]/Switz.....|Basle........ XI 
and A. Grob and F. Straub/Switz..... Basleas cia sas VI 
XXIII 
ANG ya WUT RICE alsice «0s 5 Switz..... Baslescas soe XI 
and Carl Jagerspacher ... |Switz BSasleg cot a 2 VI 
and Hans Kappeler ....... Switz..... Basles. ssc. VII 
and Herman Kraft ....... SwitZn oe Basle. s. 5 css VII 
Epstein, Wilhelm (see E. 
iOtE NUE GR aaa wiine coins’ Ger... ..0.. 
and Emil Rosenthal ..... CSOT, cens c] ove eens ooe es XV 
WOUN GEER a csc cs en exes Geta a teas Hochst....... XVIII 
UCD ate at Zo e.cid « sielescee ciel ss Gets sone: 
and Leopold Specht ...... Aus.-Hng..|..cceseseress XXIII 
Erber, Josef. See B. Homolka. 
and J. Wagner , 
Erdmann, Ernst ............ Ger....... Berlin....... II 
; XXII 
and Hugo Erdmann ..... eS Sree Berlin......- XXIV 
Erlenbach, Arnold ........... Ger....... Berlin......- II 
XXII 
and Karl Marx ........, en eee Berlin....... II 
XXIII 
Erlenmeyer, Emil ........... etc cers Lee see eeeeeeee XVIII 
Ernst, Otto (see F. Schmidt) .|Ger....... Hochst....... VI 
and Gillis Gulbransson ...|Ger....... Hochst......- VI 
and Heinrich Eichwede eo ee Hochst......- VI 
and Carl Pretzell ...... SU Ger eas: Hochst....... VI 
and Karl Schirmacher .. |Ger....... Hochst....... VI 
and Franz Scholl ......, eT ae Hochst....... a8 
Evans, William IL. See H. L 

Trumbull. 

Fabrmann, Alvin .....+6.:.+> eT ey ee Badische..... XXIII 
Fahlberg, Constantin ........ NWN, Y;. List (%) XXIV 
POT PAC ad CO lineéee cnecs «« « Switz... [cre rcrs eee ae XXIII 
ag vo WO pend ede a 1S Ep OR ee Ne er eal XXIIT 
eC Ga aaa ROE ahaa th Peri ee ea XXIII 
Peuriny enty Co. eee sn kets Uo NR OR TIE vai XXIV 
Penner, Henry J... 5 dsc cs ces Beg.s..<.. 

Bac lerratticn Versmann ..{Bng......}°c%e" 2" *s*"** XXII 
Fette, August. See J. 

Oppermann. 

Fiebiger, John H. ............ Notts. aca] sects ee xs XXIII 
UE ACES Cee ey ee (Oe VI 
Finch, EO SR ae a ee Dis eh os sete Hercules..... XXII 
Finklestein, Philip ............ N. Y..... Jecersssccees: XXIII 
WAOTIG GOED ok ee acct es es> DA. assets [te oes ws XXIII 
Fischer, Arnold. 
See R. E. Schmidt. 
Fischer, Charlies H. .......... Ney... see e ese reeees xx 
PROM OMe PE) vices ok cs Ge ws e 00.4 Cette. os Boehringer XXIV 
and Josef von Mering ....|Ger....... Merck......- XXIV 
Wischer, Eugeti ..:........... Ger....... Hochst....... XVIII 
XXII 
and Julius Oppermann ..../Ger....... Kalle... as VII 
Fischer, Friedrich ............ Ger....... Bayer.......- XVIII 
and Hugo Guntrum ...... (eeu Ses, Elberfeld XXIV 
Fischer, Max (see J. Schmidlin) state! ste Geigy....... XXII 
Pee OE UAC a we Cis vc nae Gere... Hochsti2.:. 2. XVIII 
XXII 
XXIV 
Fischer, Paul (see P. 

Thomaschewski) ............ ereh ose: Bayer........ III 
PSC ET te RICH ATG Wis ccs a s's ous aves Gertie pes Paver ina ccscs XXIII 
Fischer, Robert. See L. 

Schutze. 

Fischesser, Alfred .........6.- Geli gases 
and Joseph Pokorny ...... Getrenwa Fischesser XXIII 
Pian William (He s.c. eee os PSOE Fadi oat iva vie a sigs ses XXIII 


898,452; 994,988; 997,766; 
1,081,898. 

(In) 1,026,574. 

1,188,259. 

1,221,849. 

(Az) 1,213,608. 

1,227,407. 

1,237,183; 
1,259,499. 

940,586. 

899,863; 


1,242,536; 


899,994. 


681,689. 
473,453. 


(An) 633,438. 


923,635. 

869,073. 

(£) 658,769. 

992,947; 1,105,554. 

(Ab) 1,144,325. 

1,105,501. 

(Ab) 1,144,181. 

310,128. 

610,349; 679,221; 714,882; 
714,883; 830,312. 

858,065. 

978,865; 983,486; 
1,012,619. 

888,981. 

667,935. 

739,069. 


(An) 661,858. 
(f)319,082; (m)343,803. 
1,043,582. 

1,279,679. 

(Az) 582,853. 
(m)615,828; 615,829. 


126,277; 130,909. 


1,383,092. 

1,383,710; 1,383,711. 
1,311,158. 

(Ab) 542,046. 

(Tr) 171,787. 


203,130. 
(m) 667,388. 
(m)773,251. 
283,766 
278,926. 
540,427. 
325,827; 325,828; 329,636; 
329,637. 
(p) 729,054. 
1,338,363; 
1,340,603. 
248,153; 248,154; 252,202; 
252,203. 
270,045. 
(m) 273,498; 


938,565; 938,566. 
(Az) 1,057,137. 


1,338,364; 


276,796. 


(Az) 457,488. 
(In) 175,829. 


544 DIGEST OF PATENTS 


DYE 
PATENT NUMBERS mide ASSIGNEE GROUP PATENTEE 
Bisher, CArthtir Wiese «ater o sieisa ie | Path de kee Ws Ce Pe Us Ane XXIIT} (Tr) 1,209,423. 
Fisher, Mary Me) iitalmie\ehalelareie le,evel'e Mo Me eee Wael SER ate hee atataie BiahibC ae XXIIT 721,290. 
Flachslaender, Joseph (see K. 
Po 2Gralert) oles fae erties ate Geri. Bayere neice XV 935,009; 1,113,766. 
K. P. Gralert and Max Buff ee are Baye? cara a XV 1,081,598; 1,081,599; 
1,081,600; 1,081,6013 
1,081,602; 1,093,259. 
Synthetic.... | XV 1,132,022. ek: 
and | Pal Ge elsiste treet cre's (Zersae eet Synthetic.... VI 1,215,359. 
Flemming, ) Paul o.oo Geena OR PEAR bone e Ge mr XXIV |} (m) 1,036,087. 
Flett, Lawrence H. See C. G. 
Derick and W. M. Ralph. 
Phek, oy 755) Bmil oc 20. ce sales Gene ca ol te seas saetetion XXIII} (In)671,994. 
Fodor, Otto. See E. 
Kopetschni. {RS Spel 
Forel; “Sylvestre. o. ae sicw:siero are eth ath Ga ole cates eee VI 386,192. 
Forger, William <.0 7.602 os 35> We Sk aha etl ae Cac eee XXITI1| 776,830. 
Fourneaux, Emile A. ........ Niet Yaeee Metzger II 739,071. 
V 726,667. 
VI_ | 728,388; 728,455. 
XR (Su) 714,687. 
Badische..... XXIII) (Az)913,633; 913,634. 
ERE. dea L decent ee XXIII} (Ab) 1,277,056; Re. 14,824; 
1,350,600. 
Fowler,. Galbert a). ‘fea. ee sects 1D hdr e Hiner, AARP eer XXI | 954,949. 
Fox, Charles (i; (and Mary 1.3) Calit.. 5, <4. «semen eee XXI | 81,992. 
Frank, AIDEN clock oli lern eine Gerkg et yl Se ainee ose VI 320,638; 329,639. 
Bayetoecse ee VI 401,024. 
Franke, Charles ............. N. Y...<«. |Hoffmann,...| XX oes see 
Hrankey;Bimil cee as ce sce ks Getcs ar: Griinau...... XXIIT} (An)965,804. 
Prascht: “Fang -tAe s,s ets Ohio... .: Grasselli..... XXI | 518,980; 518,990; 518,991; 
518,992; 519,036; 
1,308,060; 1,323,263. 
Freimann, Hans 4.0... 02.... GOt eee Jager........ VI_ | 1,006,929. 
Fremery, Max, and Johannes 
Ushan fo on oe Ger, fe ccee toteamen steenee XXIIT| 650,715. 
Friedlaender, Albert .......... Exel aioe Horowitz..... XXTV | (m)966,820. 
Friedlaender, PR ta ete ee GETS cto sours Oehler....... VI 361,404. 
Kalle ae ccni VII | 819,348; 850,827. 
and Bernhard Priebs ...... ey AS Oehler....... VI 375,930. 
Friedmann, Hermann ......... ts pei K Bayer.....+.+ IIL | 1,022,781; 1,023,248; 
1,034,895} 1 1034,896; 
1,065,440. 
Hrie¢e, Jon @Wa cvoe ee pi Fa, Greiner ew hice Oa XXIII (In) 807, 453; 1,341,637. 
; XXI | 1,266,577. 7 
Fritzsche, Hermann .......... Switz: 0. | DaBlGn a wcccee VI 1,316,781; 1,325,841 
(see E. Anderwert) 1,362,936. 
Frohlich, Jaroslav. See G. 
Engi. 
Frohneberg, Wilhelm. See R. 
Herz. 
Fuchs, Frederich 40.5.4 3... 2% AFOES «he's ..|Hochst....... | XXII | 641,100. 
and Hermann Gussmann ..|Ger....... Hochstafa....3 XV_ | 626,807. 
Fuller, James Wo Minn, 625. svete ee coeee] KX | 553,556. 
Funckeg\\ Fritz) 20 ae Switzeee Basleun.ss aca XVIII | 887,620. 
and Carl Jagenspacher ....|Switz.....|Basle........ VI 1,237,192} 1,237,193. 
Funk!) Casimir coc. ees NGS racae 
and Louis Freedman ...... ING INV cis ters Metz corre XXIV | (m)1,472,208. : 
Fussenegger, Ernst .......... GEt seo nre Badische..... VI _ | 806,077; 1,034,898; 5 
(see V. Villiger and P. : 1,076,756. 7 
Julius) F 
Fussganger, Victor’ ..asse.0s6 Géti Acne | ROCKEt eins IX | 932,266; 955,080. F 
II _| 796,715. 
XVIII 816,457. 
Gabler, Max. See G. 
Wichmann. 
Gams, Alphons . wee eeeceeeees Swit?.. .-a.1 Haslet apes oe XXIV | (m) 1,336,052. 
aud Otto “Kaiserv, 57... <e. Switz..... (Baslesoue ewe XXIV | (m)1,378,343. 
and: Ernst Wybert. 4.0 4.3 Switz... | Basle. cena ey XXIV | (m)1,423,101. 
Gans, Geo Sw eee eee Getearaani: Cassellaz eer VI 442,360; 454,645. 
and Meinhard Hoffmann . |Ger....... Cassella...... VI _ | 501,500. ’ 
Ganswindt, “Albert... 0.5 asin ous Geri as cedtakee. coe -.| XXIIT| 568,344. 
Gartner, Rudolf Veecuae stories Ger. Fons ce 
and Georg Kohres ........ Genes Synthetic.... | XVIII} 1,140,575. 


Gassmann; | Charless- ane ae oe Gerzeni Soc. Chim... | XXIII} (Xa)643,265. 


PATENTEE INDEX 545 


COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
TGC MRICHAEO Moctsire estes) cls sons o's Geriena en Cassella.%.. 1 VI 1,020,756. 
Gaumer, Max. See VU. 
Kaltwasser. 
NGS Ee NVALIDCLIN cla cc cicic eves Geren Badische..... | XXIIy} (1s) 1,027,836. 
eNO MOGGIDN sc. c eyes ss ss Switz..s «: Geigy tesa ss XI 410,733. 
Geldermann, Hugo ...........- Geri Berliners etascore II 800,735. 
VI_ | 676,494; 676,495; 880,292; 
880,293; 943,536; 984,900; 
1,011,770. 
XII | 982,050; 988,870. 
and Fritz Ackermann ..... OCT eee Berlin. .:;.... VI 1,086,155. 
and Ferdinand Hass ...... FETT ak ie Berlin: . 26... VI_ | 1,166,346. 
and) Helix Meyer 3.2... <. .: Reet veers Berliners VI 1,411,245. 
and Heinrich Oster ...... Gen ore n: Berliners. VI 983,132. 
Gerresheim, Hugo ............ rar gE cai ng I gen te i XXIIT} 691,132. 
Gershon, Victor P. See E. A. 
Lloyd. 
ss BOP, LS 7 er DUAN teat Ia Rane gicatt a ce VI_ | 1,033,310; 1,157,525; 
1,281,938. 
(sbbons, Willis A. .<...0.<0... N. Y..... |Amer. Rubber| XX _ | 1,332,982. 
cabose Parry Docc cance ess alts. ois dui Pontes .c. XXII |} 1,444,068. 
(see J. A. Ambler, C. U. S. Govt...} XXII | 1,456,848. 
Conover and H. F. Lewis) 
RSCOTESET, SIPUTO) S565. ch ee es WROUWAY J a5 | oe clean we ee. XXII] 1,326,045. 
Gifford, Livingston-.......... 1s ae a ate Badische..... VII | 617,651; 617,652; 619,883; 
619,884; 620,442; 621,652; 
622,139. 
Gillpatrick, George F. ........ NEOs. nna Devoe....... XX 1,224,737. 
Gilroy, Franz. See K. Thiess. 
and G. Kranzlein. 
Gilson, John L. See C. M. 
Grant AdowC F | Nt) 
irard, LAS ate eis tal egal siier cisco ese Macnee etree aperel WES svecele ets T t) 669,030. 
EES ic DN ee Geren Sic: Berlingo. = ou 736,380; 738,027; 741,030; 
aveay 813,643. 
xX u)772,931. 
ana Paul Dieterle ........ EE OOas ns Berlinvercenscs So 934,302; 934,303. 
ana. Otto Siebert  ....... - Crete ater tcis Berliners aoe VI 741,029; 743,071. 
Gmeiner, Max. H. See B. R. 
Seifert. 
Gnehm, Robert ;.:....5.2....- Switz..... Basle........| XIX | 402,436; 425,504. 
XXII | 315,932; 322,368; 361,690. 
and Jakob Schmid ........ SWwitt. a2 5 Basleo. casas: iv 488,430. - 
VI_ | 491,422; 493,583. 
XVIIT | 478,005. 
XIX | 413,048; 413,049; 413,050. 
von Heyden..| XXII | 427,564; 427,565. 
Re PTICT as ae cas chs escece INOLWayeon| soso ie XXII lis416,284: 
Riperel, ESTEE Pies ce eset. oe Gers. 2, Elberfeld.... XV_ | 653,670. 
Goldsmith, Byron S. .......... Eh Goss pana Mack oe OO at ane XXIV | (pl) 1,375,959. 
Goodmat® Nathan ............ 
Sau pemiemimn Grobman |..jN. Y...-. |i.ceccccecess XXII | 1,314,138. 
Gorke, Herbert Beeivatnrsie ns Ve 5% » Gers: Bayeficccve cs VI 999,713. 
Gottschalk, Louis ............ ION ccotiye ss rian eee a XXIV | (pl) 1,323,589. 
OU1G, Davia By coves aes IDastedcvrce Barrette... XXII | 1,431,394; 1,441,417; 
1,448,688. 
paeete Sts thay By, Caro) <.; ae Robes ante 
an . Jiebermann ...... Visto e ror ckere! ltemare ete, te etere aeve xs Ill 465; Re. 4,320; Re. 4,321. 
Tile Who Ts 7S eee rr a Gertie. si ieee a 5a 
(see J. Flachslaender) 
Max?) Butt ‘and J; 
Flachslaender .......... Or er a Synthetic...; | XV. .|°1, 342,445, 
Pavereereicces XV 1,126,630: 
Ente Os | oe Se a WS OL Se iriatin 1 aie oa oaierele mis VI_ | 253,508. 
Ret L-CODGINS 5. os cic ice cess ING Visi oet eee [tree eee ance XXI | 203,140. 
Gfatnx, pobert He osc... ERASE es ote ide ae we oe XXIIT| 41,066. 
Grattan, Geo. E. See Geo. E. 
_ _ Matheson. 
Graul, Otto J. (see R. J 
oy, 2 Oh Ee ren Ger....... Badische..... XXII | 765,576. 
Grawitz, William J. S. ...:.... Bivona tipe eee mee te or II 193,158. 
XXIII} (Ab) 577,295. 
Green, Arthur G. ............. Eng... «<4 Brooke rect VI | 515,764. 
IX 1,200,171. 
XXIII} (Ab)950,516. 
and Thomas A. Lawson ..|Eng...... |Brooke...... VI 500,761; 500,762. 
and Alexander Meyenberg.|Eng...... |....eeeeeeees XV_ | 641,587; 641,588; 641,589; 


641,053; 641,954. 
Clayton... .. QIN KEST DKA BEE 


546 DIGEST OF PATENTS 


ah 


PATENTEE Re ae aree PP OASSIGHERY Stn antic PATENT NUMBERS 
Greppin, Edward ............ Switz + eigy eles ee XVI | 368,716. 
Gressly, © Alited 22). oc.nn ene fel KCL en wo eae Cassella. >... VI | 903,284. 
Grieshaber, Fritz. See G. Engi. i 
Griess;John tee one ans e Macias sere Badische..... vi 213,563; 213,564. 
Grimmer, Joseph ............. Switz 
and. Fritz: Straub: $24.3 <.% ¢ Switz. os.) ) Besle.ccs anes VI 1,402,350. 
Griswold, Robert G. .......... Mass....-- 
and Wilhiam: T. «Denovan '.j Mags.....slaseaseacas cs XX | 824,294. 
Grob, Armin (see G. Engi) ....|Switz Baslesca: sca VI 1,394,823. 
VII_| 891,690; 904,867; 915,346. 
anid ‘Carleton: C.c Agama ctN, Jiccs sails ws acer 6s axe XXIII} 1,422,564. 
and Jakob Wiirgler ...... Switz Baslez aces. III 1,317,160. 
XI | 1,268,455. 
Grob, Walter. See B. C. 
Stuer. | 
Groff, Charles R. ...........- Minn..... Laundry Blue | XX_ | 826,567. 
Grossmann, Eugen ............ Switz Geigyy. soe XXIII} (Az) 657,767. 
Grousseau, Edouard de. See|Fr........ 
de Grousseau Edouard. 
Grubman, Benj. See N. 
Goodman 
Grin, Gottfried is. seas eons Gers cole Bayersc yas XXIII} (ATI) 396,692. 
Griinbanm, Max? i. ieee oe Bw itZixivn.c Basle... jccvet XXIII} (Su)o901,705. 
Griinhagen, Heinrich ........ Geran’ Berlintecwses I 1,255,739; 1,255,740.) 
1,473,550. 
Chem. Found I 1,455,486; 1,455,487; 
1,455,488. 
Griinhut, Jacques .........0.- PNG ey cathe te Re nari XXIII} (Ab) 391,315. 
Griittefein, Wilhelm .......... Gers. cass Synthetic.... | XXIV | (m)1,305,462. 
U. S. Govt... | XXIV | (m) 1,338,297. 
Gtinther, Alfred. See A. 
Thauss. 
Gunther, Fritz C. (see P. 
J Whigs) Ounce ceca see ee Geriitss ss Badische..... VI_ | 798,008. 
XVIII | 1,430,899. 
XXIV | (m) 1,412,937. 
Ginther, Oscar (see I. Hesse 
andi K. Desamatri) 22....%.. Olver ce si Bayeracetes VI 839,382; 1,019,321; 
1,009,740; 1,009,741; 
1,074,429. 
Synthetic.... | wy | 1,150,675; 1,159,375. 
and Leopold Hesse ...... SEP. aga a4 | DOVER eee VI_ | 877,643; 877,644; 897,529; 
898,217; 921,105; 
Re.13,121; 921,230; 
Re. 13,422; 935,010; 
935,017; 935,018; 945,780; 
989,000. 
and Arthur Zart .c.cus ess. ECS Ny Synthetic.... VI | 1,101,739. 
and | la eilesse bre eee ae Gerinries. Bavyerooe cece VI 978,580; 982,952; 982,953; 
. 982,954; 982,955; 989,001. 
Gtrke, Johannes H. O. ........ Werte Hichst!....-4 VI 249,926. 
: ‘ XXIII | (An) 261,600. 
Shia dtr eee: ee Rieia al anel GARE ede Ad cue setae XXIV | (m) 1,417,167. 
an FNSCHELUG EA. ete witz Hotmats cosas m) 1,308,413; 1,308,414. 
aera! Gillis (see O. A ae et 
TUSt) iS siete eae ee ea ee Getiox ness Hochstein. ,109. 
Guntrum, Hugo. See F we gee 
Fischer. 
Gussmann, Hermann (see F. 
Pachse32 io 2 3o eae pees Getic es: Hochst....... XV_ | 657,768; 657,769; 660,770; 
r 671,908. 
1,000. | 
Gutzkow, Hermann (see J. xe 
Brosinery Wy case ae eae oes Lis Metin Hochst.<....« VI_ | 613,920. 4 
and Benno Homolka, ..... CPOT SS esse Hochst...2 6.3 XVIII | 661,800. 
663,225. 
Haagen, Albertaynsccesenies Geriati chs esos eee ere 693,703. 
Haager, Ernst. See C. Ris. 
Haas, Ferdinand. See H. 
Geldermann. 
Hadas; LouistaAok cris cuacseas Geren ue Badische..... XV | 718,342; 931,598. 
: Cassella...... XV | 919,572. 
SoccVArm secs XV_ | 1,329,898. 
XXII | 1,423,494. 
Hagemann; Karl cd.aneceene Cis Oppo Synthetic.... VI 1,114,750; 1,127,234} 
1,270,290. 
and OStanwe tans ool Ger ientins Baverovann os VI 843,808. 


PATENTEE INDEX 


PATENTEE Saher ASSIGNEE 
Hagenbach, Hans ............. Switz..... |Geigy........ 
Hagenbach, John ............. OWikt..\c'. 5 Geigy /¢....+% 
Hagenbach, Rudolf. See W. 

Dollfus and G. Kranzlein. 

REAM TACO 5.55 «Chesney euros INESIY «cies crareto eter atel cc oreloretenatats 
Hahnenkamm, Wilhelm ...... Gerkoce. ce Hochst....... 
Hlatlers michara OF Ps 2c... 1Ger.... sss Badische..... 
Haller, Herbert L. See E. Q. 

Adams and R. R. Williams. 

Halvorsen, Birger F. ......... Norway 

anpowcr es HOorpyeee.. 6cn ca NOT WAY scab oes cece eeere 
Hamburger, Alexander ........ 1S eee pee Bayer... oe 
Hamlin, Marston L. ...... tow it, CO Sains Amer. Syn... 
Hankel, Martin ©... ..ccesces- Get a. Griesheim.... 
ee CLE a oras wie wh he <1 AUS... uso] aciesstaicnooes 
Hansmann, Otto. See W. 

Herzberg. 

Harger. Rolla No sce ses sess D.C U. S. Govt 

Biariey, James (ciacecccnccees INE ASS yet ie| arere sie sisteters sie 
Harrsch, Eberhard .......... IN CEN A ea lictes crete skate 
BTOLE ADE Is bine sca ees os Beng. 6 le beck ss oe e's 
ES DF | A nein Ora eae i 31 ae Stewart...... 
BEALE FOUTS Da, staciecsiumes vee es Wl ag5.0 Sena bese se keane es 
Hartman, William W. See H. 

T. Clarke. 

Hartmann, Christoph ......... Meg nn FIGGHSI 7. oy 3 

‘ (see J. Herbabny and E. 

Hepp) 

Hartmann, Max, and Max 5 
SEIDELEN Gi asicietet ders toe scctvcwiee . | Switz Basle........ 
and Hans Kagi ........- Witz sa... Basle:....... 
and Ernst Wybert ........ Switz Baslevew oo ns 
Hassencamp, Ernst .2........ A) ean Dickerson 
Hassencamp, Hugo (see R. 
COU Gees ter chinks aie. fed sco a e.5 0 6 Gere Bayet.....:. 
Elberfeld.... 
HMaugwite.. Rudolf ......4. 605, Gereene. Bérlitizs so... 
Hauptmann, Peter ......... Ger....... Bayer. ste 
Synthetic 
and Albert Rohde ....... Berek 3 « Synthetic 
Hausdorfer, Arthur .......... Gere ton. Elberfeld.... 
and Carl Heidenreich ....|Ger....... Baget ess... 
and Friedrich Reingruber .|Ger....... Elberfeld.... 
Haussmann, Emil (see R. 

PAPI ee inate es % wks 4 Sap e s 5 wie Berlin....... 
Piawierek, Josef Po. .c nesses EG oats 's Sal a git ean se hs ae 
Haworth, Walter N; ......... BCotien< ss 

and Frederick W. Atack ..|Eng...... [...-.-eeeeees 
Heidelberger, Michael. See W. 
A. Jacobs. 
Heidenreich, Carl (see M. Kahn, 
M. Ulrich, A, Hausdorfer 
OE a a eT ng Ger......- Bayer........ 
Synthetic..... 
Bayerins srs 
and Eduard Martz ........ Co eee Bayeryoy i ae. 
Heim, Friedrich. See A. Stock. 
Heimann, Heinrich .......... C05 ene Berlin....... 
(see W. Werfberg and W. 

Herzberg) 

WAG LP au VitCk  .as sees ss Ee Po hy Berlin sss 


Heitz, Charles. See A. 


Dachert. 


547 


DYE 
GROUP PATENT NUMBERS 
XIX | 1,194,380. 
YI | 790,363; 790,364. 
XII | 808,919. 
XXIII 404,193. 
XV_ | 1,083,489. 
XV_ | 690,271. 
XV 1,310,751. 
III | 1,059,607. 
DIVG 171, L1S, foo. 1,015,159. 
XXII | 1,309,683. 
XXIII} (Az) 1,200,726. 
XXII | 1,384,615. 
XXIV | (p)1,297,685. 
XXIII] 170,626. 
XX _ | 88,291; 90,359. 
XXI | 1,362,879. 
XXI_ | 1,399,014. 
XXIII] 429,131. 
TII | 704,798. 
XXIV } (m) 1,403,117. 
XXIV | (m) 1,437,802. 
XXIV | (m)1,350,408. 
VI 981,132; 381,471. 
XVIII | 331,964; 331,965; 498,471; 
501,069. 
XVIII | 611,628. 
VI | 999,558; 1,209,154; 
1,405,687; 1,419,500. 
958,640. 
VI_ ! 1,073,754; 1,074,946. 


VI 1,199,890. 


VI 1,113,622. 

XVIII! 676,555. 

VI 980,251; 980,521; 1,021,364; 
1,021,365; 1,021,366. 

XVIIT] 999,028; 1,026,089. 

XVIII | 647,260. 

XXIII} 661,985; (Su) 665,737; 
953,008. 

XXII | 690,724. 

XXIII | 1,426,380. 

VI | 891,931; 944,328; 1,009,745; 
1,025,267; 1,474,587. 

VI 1,183,378. 

XXII | 902,150. 

XI | 895,635. 

V 872,815. 

XV_ | 1,096,715; 1,098,259; 
1,098,260; 1,105,515; 
1,199,697; 1,251,368; 
1,251,369. 

XV 1,099,039. 


548 DIGEST OF PATENTS 


PATENTEE papi ASSIGNEE saat ahs PATENT NUMBERS 
ak ON ART: Snes ee CET lan cre Cordessts. cus XXII | 722,506; 722,507. 
ee eas XXIV | (m)671,135; 709,321. 
Helmert, Bruno. See I 
Rosenberg. 
Hencki, Mu Vintners toreanvacuntcra borers (Erne Badische..... III 443,402. 
Henke, Clyde O. See O. W. 
Brown. 
Henle») Brang ote cue Saleen s Gere nes Hochsta eeu III | 980,602. 
forrest Naa: See E. 
Michaelis. 
Henry; Charleston 1 ya. ee ceee ET Fe ee Gleaner ntteeatanectes XXIII | 835,754. 
Hensmann, Otto. See W. 
Herzberg. 
Hensmer, Karl. See A. Blank. 
and W. Neelmeier. 
Hentschel, Willibald .......... Geraee nes von Heyden..| VII | 712,190; 737,836. 
Hepp BE duardies iy ate eee se Getic ee QOehlencn Seats V 466,826; 466,852. 
XVI | 270,311. 
HOCHSE ae eects Til 711,310; 713,432. 
and Chrisoph Hartmann ..|Ger....... Hochst... ss2.). III 734,866; 748,375; 975,863. 
and Rudolf Uhlenhuth ....|Ger....... HGchstis ¢..55 III | 778,036. 
and Rudolf and _ “Fritz 
Reemiertie a 2s CEeRe aes Ero Genes ELOGHSE Sus «ote eg III | 1,052,480. 
and Ernst Wolpert ....... Gris. Hochst... .2: III | 754,768. 
Hepp, cnichard oct aes ee Gare. Oehlet i... s.: XVI 1 -270,31% 
Herbabny, Julius (see C. H. : 
Rudolph) Capea Sapa Giae EC. ea as Ochlet i.e. «2 VI_ | 639,042; 644,201; 644,202; 
666,866; 666,867; 670,308; 
666,866; 666,867; 670,308. 
XII | 627,600. 
and Christoph Hartmann ..|Ger.......]..scccessees VI 639,040; 639,041. 
Hermann, Willy. See M. 
Mugdan. 
blerimarne, (eo). <i awe oe eee eo Pr ee ELOCD SU erie XXIV | (m)1,285,703. 
Herre, Alfred and B. Jaeckel .. 
(see B. Heymann and W. 
Bassey Pooper tate Ons Ser Pe Pelee Bayer. we yas XV_ | 895,637. 
Hermann, Albert. 3 secs oe oe Ger tye: Hochst... (tc XVIII | 412,613; Re. 11,077; 
412,614; Re. 11,078; 
412,615; 422,018; 
Re. 11,116; 437,989; 
453,477; 463,808; 490,408; 
567,567; 580,186; 580,187; 
580,188; 628,243; 630,224; 
639,976; 639,977. 
Hertlein, Hans. See M. Moest. 
Herwig, Felixo\; i>. te ae eer iaaee Elberfeld.... | VI | 673,079. 
Herz, Richard (see A. Weinberg 
and I. Levinstein) Ef BAS Cassellas.s +. IIT | 1,103,004. 
VI 1,107,164. 
XV 709,151; 723,154; 742,189; 
956,348; 966,092. 
Sek Meee ete VII | 1,243,170; 1,243,171. 
ands Hs Balhorne eee CAPT are Casscella esc XV 1,452,805. 
and Wilhelm Frohneberg ..|Ger....... Cassella...... XV_ | 1,100,877. 
end W.saul Gas eee Gee rivaies 5 Cassella...... XV_ | 960,919. 
Herzberg,s Martin <1 Geeseces GES; ot aes Davers.s) ses VI_ | 384,315; 384,316. 
(see A. Blank, F. Runkel 
and M. Ulrich) Elberteld: o.. VI 792,032; 792,033; 792,034; 
79757313 7975732. 
Synthetic..... VI 1,126,466; 1,160,406. 
and Friedrich Runkel ....|Ger....... Bayer........ VI_ | 953,033; 953,034; 953,035. 
Herzherg, Withelar). ) 0.2... 5. GET. 5 ss sie Berlin..:.4% sas VI_ | 800,914; 842,548; 987,362. 
(see O. Scharfenburg) : XXII | 536,524. 
and Walter Brnuck........|/Ger......-. Berliny i: a6 III | 993,992; 1,008,906; s 
1,008,908; 1,050,829. - 
; XV_ | 996,485. 
and Otto Hansmann ...... Strasse Berlin....... VI_ | 583,439; 657,064; 657,065. 
and Heinrich Heimann ....|Ger....... Berlin....... V 567,473. 
and Gerhard Hoppe ...... Ger oes Berlinsi hou) III | 1,078,505; 1,131,516; 
1,419,502; 1,431,656. 
and Werner Lange ...... (er. toe Berlin. .4 a: VI | 997,061; 1,078,503; 
1,078,504. 
and Heinrich Oster ....... Gertrerines Berlin ees. VI 906,422. 
andes a Ronis meses Gerise secs Berline eee. vi 954,960; 955,068. 


and Franz Schwabe ...... Ger Se eee. Berlins. avieres VI 1,008,907. 


PATENTEE INDEX 549 


PATENTEE pate ASSIGNEE panes PATENT NUMBERS 
and Oswald Scharfenberg .|Ger....... Benlinges. VI |986,287; 1,038,884; 
1,408,296; 1,408,207; 
1,419,501; 1,426,189; 
1,426,190; 1,431,655. 
Ven |e tO2.0 71 te 200, 8 SOs 
XVIII |647,834; 835,682; 866,350. 
and Max Ronus ........ Geri sta Berlin Shane ote XV_ |864,644. 
muna Otte Siebert ~.....:... Ger... .. i Berlin.\... << VI 704,825; 704,826; 770,430; 
03,592. 
and Oscar Spengler ...... Ceti se es Berlin....... VI |865,587; 906,421. 
Brews GuUatG. LHON  s s.de. 6 « Genres os Berlin. .... 6. XXIL | 800,913. 
ANd Oscars WeDer «6.4.0.0 5 Caneraece Begin earecy ee VI |541,750. 
i XVI |522,897; 539,738. 
SECA PEIOIO ove cic a <b alace sc» Geto es sce. Hochst. vs .<'e. III (668,445. e 
(see F. Scholl) V_ |673,640. 
Hess, Fritz. See E. Wray 
Pee ON ies. cv seo Tea Shire ss 6 Barrett...... XXII | 1,457,543. 
URCE NOLES henna ee an Ta eee ah Hochst......- TIl |734,325. 
Hesse, Leopold (see O. Gun- 
IN Sis) pape. Wiebas c 3s Bayer......-- VI | 1,054,348. 
O. Gunther and A. Zart ..|Ger....... Bayer........ VI |931,4233 931,424; 933,446; 
; 933,447; 933,448; 933,562. 
Hessenland, Max ............ rete eo at Hochst....... III 998,772; 999,785; 1,002,270; 
1,007,104; 1,023,847; 
1,047,940. 
Bremer ath scala hk sass ss SwitZccee |? oesee see eees XXIII | (in) 534,560. 
Heusmer, Karl. See A. Blank 
and W. Neelmeier. 
Rieger, WieWard 66 oo. ine dan oe N. Y..... |Williamsburg. | XXII | 1,330,074. 
Heymagn, Bernhard~.......... ee Bayer........ Vv 592,608. 
XVI |524,322; 524,323; 560,795. 
Elberfeld..... VII |618,096; 626,231; 647,263. 
XV_ |688,999. 
XVI _ |606,212. 
XXII |683,464. 
ANG ee ATETCG MOLT ET TEL. oe s+ (Gerreo Elberfeld..... VII |657,539. 
R. Kothe, O. Dressel 
and A. Ossenbeck ..... Gers. o. Synthetic... .. XXIV | (m) 1,308,071. 
Heyn, Herman B. See G. O. 
Curme. 
Pivibert)rearold <4. 51.5.0 c>s« ey ae Com. Res.... | XXIV |(m) 1,321,307. 
Higburg, William. See I. H. 
Derby. 
Pligwing, James) ...06scescsces Bees: i soaree ek os <0 II {138,155. 
Pivipert, ssieviried . isc. csass- ope Vnitr Sy 5 XXIV | (pl) 1,427,386. 
Hingberg, OSC@r ¢isasescsccas Switz..... |Hochst....... XXIV |(m)560,416; 1,432,291. 
PUITGCH CRODESt 2545 cca ev ccc es« eres i: St. Denis.... V_ 1|536,626. 
Hochstetter, Robert .......... GO) GIOM ee a aces orete slates VI_{1,052,145. 
PIGe I OTT es oe dave os eee, Cee Elberfeld..... XXIV | (m) 607,172. 
Hoeckel, Siegfried. See P. 
Julius. 
PIGUET, BIUWAIG, os cS scenes Gees hones geeh ahiate XXIII | (Su) 647,493. 
Hoerlein, Heinrich ........... Copeie: Bayer sess. + 6s VI |965,882. 
Hoerlin, Julius (see O. Rein- 
BERT ME oe ahs « (Cer ee ae Weiler....... XV_ |796,514. 
Hoffa, Erwin (see H. Wagner).|Ger....... Hochst... i-/07- VI | 1,197,633. 
VII |1,025,138. 
XIII | 1,197,632. 
Hoffmann, Augustus W. ...... Meet. | evenvhate nce as XVIII | 43,066. 
Hotlmann, Carl .... os 5.<.<as. (serler enc 36 Héchst....... IV_ | 720,920. 
(see H. Boedeker) 
XVIII | 615,485. 
: XIX |613,926; 675,216; 694,149. 
Motimann, Julius .......3.. i Switz:. «.<.| Basless sai III |916,154. 
Hoffmann, Meinhard ......... Roe fe ar hs Bee eae) Por VI |560,796. 
(see L. Gans) Cassella 7. 224 VI 314,938; 314,939; 332,528; 
464,135; 464,566; 472,121; 
Re. 11,267; 473,928; 
480,326; 533,463; 749,195. 
XXII |331,059; 498,882. 
and Carl Ff. Daimler ...... |Ger....... Cassella...... VI {514,599. 
and Georg Kalischer ..... Gera toct Cassellates.. XV_ | 660,058. 
and Carl Krohn ics. ec. Hoey Le Ts Paar Cassella...... VI |514,931; 516,203. 
and Arthur Weinberg ....|Ger....... Matheson.... VI {345.9013 Re. 11,598. 
Cassella... 2. VI |442,680. 
RIVETIE TT, FORO os sieieete ne Saves err ak ats Cassella...... X 4316,036. 


Hoffmann, Reinbold .......... (ONS HOES Ware Cheat XX '202,822. 


550 


COUNTRY 


OR STATE ASSIGNEE 


PATENTEE 


See R. 
Knietsch and M. Mandt. 


Holdmann, Robert. 


Holl, Alfred. See F. Singer. 
Holley, Alfred E. and O. E. 


WOR rhc ierscoietecstw icy siete ais sinlalen SS 66: Cree RANG GALS Net RECS sees 
Holiday Fomine: sec acs cutest Pence Read-Holliday 
Holliday, Lionel B. See L. G. 

Badier. 

Holliday, wRobetts ic cies sacs ates Binngiciegareh (eet saree aavine 
Holliday, Thomas’ Jy... .5.+6 <> Boole k sies.| va Oa Rete eee 
Read-Holliday 
and Robert Holliday ...... BUsigen es wom Us es eters aiaienecs er 
Holmes, Fletcher B. .......... 1 MOR Mie ee du Pont..... 
Hrojste; Aveore i aa)d ayes ee sia e ok Geraci ei. Bayets soos as 
Holt, Henry S. A. (see D. 
Vorlander and R. Knietsch).|Ger....... Badische..... 
and Karl Reinking ........ Gers,.c2s Badische..... 
and Gerhard Steimmig ....|Ger....... Badische..... 
Homolka, Benno (see H. Gutz- 
kow) Gers i gas Hochst. vem. 
and Josef Erber iss cscs c Gert eas Hochst.\<6..6 
and Friedrich Hiibner ..... Gerd ss 5st Hoechst? ventas 
and Friedrich von Bolzano|Ger....... Hochst. ccc 
and Otto Liebknecht ...... ET ee iste Hochst. ...%.. 
and Nicolaus Schwan ..... Ger... ses... Hoéchst..i.5 <5 os 
and August Stock ........ Gerinantr Hochst....... 
and Robert Welde ........ GEC He cieter ate Hochst. cece 
Hoppe, Gerhard. See W. Herz- 
erg. 
Houghton, Alexis C. ......... N.Y. Semet-Solvay 
Houlehan, Arthur E. ........ Delus.cenk du. Pont..... 
Howald, Arthur M. See A. 

Low 
Hiibner, Friedrich. See B. 

Homolka. 

Hat, Withert 11. cee peek Pace hits Koppers...... 
Huffman, Charles .$o)... 2240. TH Aare ee Sunbeam..... 
Huguenin, Daniel EF. ......... Switz....- Durand:..... 
Huismann Johann: . ose seen Pra ee, F Synthetic..... 
Hund Walter) areas eae. Calitics Ua eee rete 
Hutziers;Rudolfi soceens ces. ers Sos Badische..... 
Ijinsky, Michael i...ess deus Gernot Poe eae 

Wedekind... 
Imbert, (Georges) va. csseedewere COT os taracltatehe cata ehereees ete 


DIGEST OF PATENTS 


PATENT NUMBERS 


1,297,170. 
250,247. 
(Tr) 51,404. 


(Az) 439,953. 
355,934. 
362,835: 
386,247. 

(Az) 252,317; 271,636; 
355,933; 355,935. 
(Az) 241,661; 254,550. 

(e) 1,309,577. 
1,012,853}; 1,059,670. 


643,502; 661,871; 713,437; 
715,074; 1,042,679. 

661,872. 

(In) 820,869. 

(In) 826,428. 

(pl) 1,294,662. 


1,209,163. 

458,281. 

649,727; 649,728. 

669,794; 675,217; 726,688; 
894,004; 894,005; 894,006; 
898,738. 

844,804. 

471,638. 


575,237- 
(AI) 418,916; (In) 702,730. 
763,756. 
871,507. 
839,590. 
675,217. ; 
712,798; 768,455. 
704,804; 714,000. 
(p) 767,815. 
622,854; 636,043; 636,094; 
640,564; 648,261. 
894,004; 894,005; 894,006; 
943,678; 1,025,174. 
893,499. 


1,308,757. 

(m) 821,291. 

1,308,356; 1,334,033; 
1,337,317; 1,392,042; 
1,477,058. 


1,416,205; 1,416,206. 
1,274,046; 1,274,049; 
1,283,519; 1,413,026; 
(Az) 1,274,047; 1,274,048; 
1,315,961. 
(In) 411,149. 
1,159,386. 
1,365,407. 
(In) 780,886; 
1,188,543. 


1,133,031; 


778,670; 851,423. 
826,509; 826,510; 847,078; 
996,487; 1,087,293. 
1,261,394. 
(An) 1,199,273; 
(In) 1,175,634. 
894,149. 
894,148. 


: 
j 


PATENTEE INDEX 


551 


COUNTRY 
Beamer merer, Garlic... ess Te Badische..... VI_ | 863,396; 914,144. 
(see P. Julius, L. Blangey XXIII | 833,602; 1,232,551; 
and R. Bohn) 1,232,552. 
Az 058; 872,181. 
Iserloth, Carl F. See G. A. Led apoio Si” 87 
Waldinger. 
elervt ax 0ET. d.crcrs wikietele, «sha «6s 
(see O. Bally, “C. Miiller J 
and R. Scholl) Géticc. «+s LDadisene.s.<. III | 617,686; 619,574; 621,679; 
650,756; 688,645; 690,292; 
715,622; 738,614; 798,104; 
814,137; 831,002; 837,840; 
855,248; 860,480; 876,190; 
893,508; 909,800; 922,282; 
929,442; 1,001,408; 
1,004,433; 1,026,588; 
1,032,215; 1,032,216; 
1,047,812; 1,047,813; 
1,057,243; 1,062,975. 
III | 1,089,221; 1,090,621; 
1,126,475; 1,169,404; 
I,201,968; 1,207,762. 
ys XXII | 619,181; 828,741; 893,507. 
Bie Prt) eet cals ce es | GET... es Badische.....} III | 863,397. 
and Hugo Wolff ....... Geto ete + Badische..... Iit 929,443; 961,612. 
Arthur Luttringhaus 
and Heinrich von Dies- 
on) Cs 2 A eee Eee aa ete Badische.....] III | 941,320. 
Israel, Adolf (see A. Blank, K. 
Krekeler and P. Ott) ...... 
and Oscar Dressel ........ Geri. coe Elberfeld.....} VI 731,460. 
and Richard Kothe ...... Cette ss << -|Elberfeld..... VI | 614,301; 648,623; 658,807; 
662,122; 663,498; 675,620; 
675,632; 677,516; 677,517; 
748,076. 
XXII | 653,678; 656,646; 675,627; 
Ah eay 675,630; 675,631; 
77,514; 677,515. 
and Karl Bathe A ee Ger... Bayer...... VI __| 515,3395 543,539. 
Iversen, -[..-0. attare ifnte a's ws NV IRS a wanes De tate Sale yatarw Som ec XXIII | 83,502. 
Jackson, James ....... re ES | Oe ae eae vee eceeeecees XX | 155,230. 
hae MOUS ge oe ee ees sls, 9 N. Y..... |Dissosway....| XXII | 1,446,564. 
acobi, Andreas (see R. E. 
oT at ht hel ee APES ee e's Pavericcss ss -| IIL | 1,038,580. 
Jacobs, Armand M. See Miil- 
ler-Jacobs. 
Jacobs, Walter A., W. H. 
Brown, M. Heidelberger and 
IPL GRERO sod ocic eo) chases cas N. Y..... |Rockefeller...| XXIV | (m)1,315,127. 
TACONSON SEM) cec.c1es «es = bP poe WE eae tae oe teee pp WLLL 1257,7373) 1 200,585. 
Jacobson, Paul and H. Tigges haw fin en's Cassella......| XXIV | (p)604,049. 
ORE Ie RUREAE Od) cies cie'es nese ee Crete ss Elberfeld..... XXIII} (Su) 717,749. 
Naéckel, Berard ..cc.s aves: Gere: Bayer. c cer. XV_ | 898,916. 
(see A. Herre) Synthetic..... XV 1,140,745. 
Jaesschin, Hugo. See O. Kalt- 
wasser. 
Fagerepacher, Carl 2... ccc ceces Sit Z . Ge | ASO eleieie's VI 916,161; 1,210,808; 
(see G. Engi, F. Funcke 1,216,813; 1,323,285; 
and B. Wuth) 1,375,701; 1,382,196; 
1,437,758. 
Hadi Was LESICT “ens vices sss Switz Baslecrs ones ier VI 1,338,506. 
and Thilo Kroeber ........ Switz Basle. Ge ws VI | 750,284; 797,441; 
Re. 12,557. 
Jahrmarkt, Friedrich M. See P. 
Julius. 
Jamieson, David <.-.5<.-..0065 0) CER pe ieanes) re wre niges viens) | eels | Cin yaoss saa: 
Jansen, Johannes (see A. 
ime VAe Pe ho we ei eed oe. Getrag sss 
and Wilhelm Neelmeir ....|Ger....... Bayer........ VI_ | 924,231; 924,232; 933,841; 
933,842; 936,321; 961,354; 
961,355; 981,276. 
Janssen, Hermann ge ef.......|Bayer.....---| XXIV | (m) 492,868 
arosson eon an uller- 
: Pack Bue +e 2 aes Wyate. u e Brown....... | XXIII} (Ab) 134,066. 
Jeanmaire, Paul and Rene Bohn/Ger....... Badische..... XXIII! (An)772,237. 
Jedlicka, Karl (see J. Schmid) |Switz..... Bacletia.cy as I 666,095; 666,006; 730,771. 
VI | 585,104; 759,613. 
and Arnold Schedler ...... Switzucise Daslen naa eu VI 763,761; 889,016. 


552 


DIGEST OF PATENTS 


—————aaaaaaoooooooomm=QeeeaeeSaaSaS==_—__u_ec_x_—c_—c——S——aSeaSsaSsSsS=__3__je__‘uu¥>7—_=>7>x3>xzu>—sSsSsoSoaSs“scssoso(u0W—SOOOOqOoOSoSoS 


COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
Tohansen, Ernest) Moe... 2s, Eidsraierele ele Atlan tics ss tawt. XXII | 1,477,820. 
Johlin, Jacob Me Ve heains ch ose N 2a Yo Semet-Solvay. | XXIV | (f)1,372,434. 
Tob a aanSa ts. se ies oc ols iar RIS PRE SC ip Bee WM XXIV | (pl) 1,355,834. 
Jones, Whitney Bo .% sca en vat cae Butterworth VI 1,310,532. 
XXIT | 1,394,556. 
Jordan, (Heinrich? ss. ne4 see Gerrans. Bayer........ VI 999,797- 
(see W. Neelmeier) Grasselli..... VI 1,422,866. 
and Wilhelm Neelmeier ...|Ger....... BYEL Seki es VI_ | 916,323; 920,151; 993,073; 
1,000,269; 1,010,433} 
1,024,080; 1,024,081; 
1,032,412; 1,097,231; 
1,098,388; 1,114,771; 
1,127;2613,) 16547,609. 
Jorg, Paul. See R. Maag. 
Joyce, A. Willard) .i.cn dares N. J....- Chem. Found.| VI | 1,472,333; 1,472,334. 
Julius; pePaulsa(see.. tH. ZA; y 
Bemnthsoen yey. ies Crkeuitvoeee Ger......- Badische..... Vv 609,352. 
VI | 447,189; 524,251; 524,252; 
524,253; 524,254; 525,656; 
525,657; 628,814; 644,233; 
644,234; 644,235; 644,236; 
644,237; 644,238; 644,239; 
650,7573 654,064; 654,065; 
656,120; 677,227; 677,228; 
677,229; 677,230; 677,231; 
688,647; 690,294; 710,059; 
Seppe 718,356; 752,562; 
33,605. 
XII | 670,172. 
XV 648.7535 6481754; 648,755; 
,646. 
XVIIT| 886,815. 
; XXII 785,003. 
and Louis Blangey ....-. Ger ee ccvees Badische cceee VI 932,289. 
and Georges E. Darier ....] Switz Badische..... XIX | 637,340. 
and Ernst Fusenegger ....|Gef....... Badische..... vi 754,315; 786,767; 787,767; 
787,768; 789,096; 792,421; 
879,053; 914,146; 921,546; 
935,371; 1,188,545. 
TX | 955,080. 
XII | 935,370; 1,010,910. 
and Siegfried Haeckel ....|Ger...... Badische..... VI | 750,716; 765,581. 
and Carl Immerheiser ... |Ger....... Badische..... VI 1,073,902; 1,073,903; 
1,073,904; 1,073,905. 
and Richara) Waiblet es. COURT A®, Badische osSee XXIII | (Az)634,824. 
and Fritz Gunther ....... eS ae ese Badische..... VI 692,676; 695,811. 
XXII | 713,447. 
and Friedrich M. Jahrmarkt}Ger....... Badische..... VI 695,812. 
and Eduard) Munch)... > ier ots. be Badische..... XVaulo20,60 5 
and Franz Osthelder ...... ee sates Badische..... VI 765,080. 
and Walter Reess ....... Ger......- Badische..... I 644,324. 
Hans Reindel and F. C. . 
Gintherors -oomie tee Ger....... Beduehosen VI | 770,177. 
and Pek euboldgem aan Ger....... Badische..... XV_ | 650,326; 650,327; 735,775 
and Akim Tkatsch ......- Ger...... Badische. 1. cee 619,577. 
VI_ | 692,675. 
ve Si sok and P. Nawia- : 
PrP at Nea pif oe S een : weoee | WIL | 955,410; 957,683; 
oad ron \Winters we eck Gercoryeaes aa pane: eat VI 765,079. 
Junius, Gustav E4i oi gee Gefitnaise Sanderson....|. &V oor 
Justmbredrichwy. yc acters Ger.2. ass THochste eee XXIII | (Az) 647,268. 
Just, Richard and Fritz Eck- 
hard cc eiccsees Ga em oe ee Gericcis xis Badische..... XXIII (An) 1,150,863. 
and Huge Wolff...26. 2s. Ger. as awe Badische..... III | 1,003,268 
Racer, Filip. 3904 0. cheese a Gefoaes ens Badische..... TIT | 863,401; 925,017; 931,618; 
(see M. Isler and H. 932,290; 1,095,731; 
Wolff) 1,459,536. 
XXIIL| (An)970,340. 
Kage, Hans See M. Hart 
mann. 
Kahl sbeopold asc. Getraseee « Rutgers...... VI (m) 1,028,074. 
Kahn, Myrtil (see R. Lauch and 
Ov Deesseys ine eee ee Get on cee Elberfeld..... VI_ | 425,885; 602,540; 603,008; 


722,715; 722,716; 725,847; 
725,848; 726,695; 727,962; 
727,963; 727,964; 727,965; 
727,966; 727,967; 729,601. 


PATENTEE INDEX 


553 


COUNTRY DYE 
PATENTEE Su eCATR ASSIGNEE | croup 
Bayerivaceiciw ste VI 
and Karl Heidenreich Geri sess. Elberfeld..... VI 
and ekRichard Kothe .....- Get. Sooke: Bayertcsewsoe VI 
and Anton Ossenbeck =| KOC aE ericr Baviertecsuren 
Synthetic..... XXII 
Baverwoncties« XXIII 
and Friedrich Runkel Getecs pws Bayer’. cee VI 
Elberfeld..... VI 
Kaiser, Otto. See A. Gans. : 
Kalbe at witiecce tetellee siecs cis + etan caren Badische..... VII 
Kalischer, Georg (see F. Klinge- 
mann and M. Hoffmann) ... |Ger....... Cassélla cn... % ae 
Se te eas VI 
XV 
XXII 
MIG Ph ISSET wi. dws o's se» trefins acne Cassellacutsjess XV 
and Nee A oo a aa Gens ss 6 Cassella ui. XV 
Kalkow, Fritz. See J. Abel. 
Kallab, Ferdinand V. ......... Serv aes Oehler....... XXIII 
Kaltwasser, Oskar (see B. : XV 
Or ae Ger....... Berlin....... XV 
and Max Gaumer ........ Geri ee cc os Berlin PAIR VI 
and Hugo Jaesschin ...... Getic sisie ae Berita ses 
and Hans Oechrn .2.....;.. (ETE SoS aise Berlintss.as II 
mamma Oliverta.s ee. ce ae fe. ws XXIV 
and Ernest H. Volweiler .. |Ill.......- Abbott....... XX 
and Roger Adams ...... Ill........ Abbott.---. *. IV 
Se Michael. See F. 
ender. 
Kate, Tehn L223 <i hee et... CR Saray | pee eee XXIII 
Kappeler, Hans. See G. Engi. 
Karczag, Ladislaus. See E. 
Kopetschni. 
WeardOa Michaels.) <3) ess. ss Ger....... Badische..... Il 
and Paul Nawiasky ....... Ger....... Badische.. ae 
Karrar, Paul. See P. Ehrlich. se 
EU 2 ne Japan..... Mitsui....... XXII 
Kaufmann, Frederick J. ..... W. Va....|Ritchie (1/10)] XXII 
Kaufmann, Ludwig ........... Berio 4 lane vdtes ys XXIV 
Kegel, E. See F. Kruger. 
Rete, OWVETHED 55s dee ec ses Ger....... Berlin....... XIV 
Elochstvecciw: XV 
Weempe Theodor sowie e ee es ewes Ger....... Chem. Fab... | XXIV 
Kempton, G. and Robert B. ... |Emg.----+ |[..--0. eee ees XK 
Kendall, Donald S. See E. E. 
Nootny. 
Kendall, Edward D. ........ wa [Ne Yeeeee [eee sees ces | XXIII 
Read-Holliday XVIII 
Renda, Henry DD. 2 foci ces: Mass....-.}....-..000-8 pr 
Kerkovius, Leo. See R. Kir- 
choff and O. Schulthess. ; 
etme oANieee ne te Nl... Switz Badische..... XI 
(see H. Caro) XVIII 
and Co 1. Miller*:........ EPs inca h Badische..... XVIIL 
etteee oli oui. dcks we Ger....... Cassella...... XXIII 
ee A. Bee H. Zoblin. - 
ansnourg, Henri, 2. 0......... Calslohe et otele Eddystone....| XXIII 
BSED Ye WUE pine ac cack oes Love ee eaten So. Met. Gas. | XXII 
RIP CHUOE, OEABETY yy cs ace we + 4 © xbfod sin s.4' Bevlinoes:.a: VI 
Birchhow, Richard ........... Gen rane te Berlineee.. VI 
XXIII 
and F. Haussmann ....... Get hence Bertin. sue rs XV 
Jens Dedichen and Werner 
ECT a ee en I Geter: Berlin. 34. »6 VI 
and Leo Kerkovius ....... en ee Berlity 23/322 VI 


PATENT NUMBERS 


936,456; 946,050; 946,051; 
946,052. 

605,103. 

843,149; 865,252; 865,253. 

935,031; 964,786; 1,000,606; 
1,025,983; 1,025,984; 
1,027,132; 1,078,925; 
1,078,926. 

1,140,747. 

(Az) 1,060,097. 

536,431; 504,996; 595,021. 

603,009. 


T,012,303¢ 


999,798. 

15,205,720 5) 1,205,727. 

813,155; 879,552; 886,985; 
999,230; 1,079,415. 

610,541. 

807,117. 

1,129,574; 

1,440,833. 


(Ab) 529,498; 529,499. 


651,077. 

736,403. 

683,119; 683,120; 684,065; 
1,003,266. 

1,416,646. 


(m) 1,331,712; 1,388,573. 
(m) 1,358,750; 1,358,751. 


(Az) 1,333,807; 
(Tr) 1,355,048. 


Lj, 200,13 45 
1,200,848. 
1,253,252. 


1,400,555. 
1,359,071. 
(m) 1,060,765. 


386,709. 


701,051. 
(m) 322,940. 
426,504. 


256,330. 
421,049. 
413,724. 


396,574. 

290,891; 290,892; 290,893; 
297,413; 297,414; 297,415; 
297,416; 333,861. 

327,053. 

(In) 1,029,066; 1,043,016; 
(Su) 678,884; 693,653. 


(Ab) 213,907. 

1,348,722. 

617,963. 

512,116; 516,604; 536,532; 
536,878; 536,879; 536,880. 

(Az) 842,560. 

635,168; 635,169; 647,846; 
647,847. 


1,219,954. 
820,052. 


554 


DIGEST OF PATENTS 


COUNTRY 
PATENTEE OR STATE ASSIGNEE preset PATENT NUMBERS 
Ricshay WHEAMUL. acme s eee mal Michio cs. DOW se ea ts oe XXII | 1,386,118. 
Kitchen, Fredrick T. .........- N. Y..... }K. & T. Chem. | XXII | 1,322;680. 
Kiteet, ES OF ©. os uie'ope)s ibisis eietas Pasi ada cd wea eka eis ae ot XXI_ | 1,254,914. 
XXIV l : 
Kiages;: -AVSUSti vans sleeyre wetems Geti micas. Col eaias 
_ and Hermann Vollberg ....|Ger.....--}oseeeseceeees XXII | 1,013,181. 
Klingemann, Felix ........... OE) ies a Cassella te wees VI 1,150,825. 
San rat Rabat 2. 
an eorg Kalischer ..... (tert bens Cagselian css ss VI |8 j 
Knecht, Oscar ......seeeseeers SwitzZ...+, Sandozaen eats XV Hae 
Knietsch, Rudolf ............. Ger tae, Badische..... VIL |524,256. 
and Robert Holdmann ....|Ger....... Badische..... VIL |677,239; 677,240 
and: Pats: Seidel op2.55 205 Gere. cass Badische..... VIL |546,165. ee 
Badisches <0.) | coe eee 
and Otto J. Graul ... |Ger....... Badische..... VII Cras: 
and G. W. Meiser|Ger....... Badische..... VIL |756,171. 
and Henry S. A. Holt ....]|Ger....... Badische..... VII 644,326; 746,965 
and Erwin Oberreit . |Ger......- Badische..... VII 646,841. igs tay 
Knorr, Ludwig a ali a etal) eaee) bin, Ger oo eeeee Hochst Me ee XXIV (m) 307,399. 
Kober, Philip Alcs oaasiconse en's We Viens (OMUINDs cas oe XXIV |(m)1,405,228 
ern Max. See F. Raschig. pec ianece 

oechlin, Horace .......+-..: Ger es ls ersceiar emcees XI 2 2I: 

__ and Otto N. Witt ......... OTs kn civil eeie ave vauces VIII AEC says 275,774 
Kohler, Bye it aicre Sloe tena aie eetee Gererreess Badische..... VI 224,927; 224,928. Sts. 
Katig, Brestucci. cna ee Geert Hochst. ...+>- VI |602,637; 602,638; 602,639; 

602,640; 602,641; 626,913. 
2 XIII 805,143. 
and Franz Scholl ........ Génictascs Hochst... 0s. XXII | 618,688. 
Konig, Karl .....--+seeeeeeeee GETS oad bie Hochet. |i... VI |878,964. 
Konig, Walter o.0205..c0ccceee (Sais caews Bayer cess ys VI_ |874,067; 874,968; 809,177. 
XIX 913,5135 91315143 947,918; 
APs : 906. 
Konig, Wilhelm ...........06. Gef.....0% Merernc tT ccs: vI me Spry 
RE a LT Se a, Ceamin nS hus a eves SAS? vi 042,916. 
Keonitzer, ‘Prank tevce Fs chess on oh Gari tis 5 al ae there eeree XXIII | (Ab)830,082. 
Koerner, Georg: 25. os ¢ eee ccm Ger, tases Badische..... VI |420,350; 638,127. 
Koetschet, Joseph ............ Besidusbins Soc. Chim VII = |662,073; 662,074; 662,075; 
662,076. ‘ 
XVIII Aa baie 
XXII 07,050; 709,159. 
XXIV | (£)648,568; 692,863. 
and Andre Barbier ..... Beye Wee Soc. Chim....]| VII [1,015,495. 
and Maurice Beudet ...... Bet wpe Soc. Chim.... | XXII |1,298,356; 1,306,963. 
Roetsie! “Arthurs: .ssccosee aus N. Y..... |Rohm, Haas..| XXIV |(t)1,344,950; 1,344,051; 
1,344,952. 
Kohlhass, Jakob. See H. Wag- 
ner. 
Kohres, Georg. See R. Gartner. 
Kolbe, Carl. See R. Schmitt. 
Kolmer, John A. See J. F. 
Schamberg. 
Kopetschni, Eduard .......... Get. das es 
Ladislaus Karczag 
and Otto Fodor ..... Gert Karczag.. oc. XXI 
Koreff, Richard ........+-..-- Aus.-Hng.. z ea apd: 
Kinzlberger... 850. 
Korndorfer, Georg ......-e000+ Ger ovaa. archi AXIL | 544,860) 
(see F. Stolz) 
and Baptist Reuter ....... Geran Hochst.cc.... 
Kothe, Richard (see P. Ott, A. ney SOT oa a 
Israel, O. Dressel, B. Hey- 
mann and M. Kahn) : 
and Oscar Dressel ....... CT...- eee Synthetic..... Vv 
and Heinrich Hoerlein ..|Ger....... Bayets sosex os ue pre 
and Anton Ossenbeck ..... Ger. ides Elberfeld..... VI 8. vie 
Friedrich Reingruber ..... Geri. Soe. 43175 
and Hugo Hassenkamp /|Ger....... Raver ciuks was 
Moritz Ulrich A AVAL ete ie 
and Oscar Dressel ..... Gerson. Bayer VI 
+) sich Heptsitcn |S TRIS PASTAS Ts ee) SRL PW aS a eR A MIO AG Gc 511,532. 
Kranzlein, Georg .........+++- Ger.oits xs Héchsts awn. x 
(see A. Schmidt) mbes 
and Martin Corell ........ Gerais oe an HSchst: ve XXIV |(m)1,422,860. 
Rudolf Hagenbach 
and Franz Gilroy ...... Gere s'ke as Hochst e's ns:2 XI 1,138,670. 


j 
: 
; 
% 
f 


PATENTEE INDEX 


555 


PATENTEE eared ASSIGNEE 
erat MELOrinan tl lsscalcic's sba'e's > Switz Baslevetaer vats 
(see G. Engi) 
Krais, Paul. See K. Krekeler. 
Kramer, Erwin and Ludwig Zeh|Ger....... Bayerwentusie ca 
Rrdaee, (Norman VWiaiisec. ss... PML Vet shasin cee mens Pisa aes @ oa 
Petes tri thie) sg cis si/eie ciele\e.e 6.0 Switzecd se Basles tees. cis 
INA Yel hion Cassellas cues 
Krecke, Friedrich (see I. Rosen-|Ger....... Krallee trons are 
berg) 
and Ignaz Rosenberg ..... EP e ne os 5 Woatle rs Pecke a's 
and August Blank ........ oe Seas Elberfeld..... 
and Adolph Israel ........ ae aes Biberfeld...... 
and Eduard Martz ....... erie cs. « Elberfeld..... 
BNMOPOUL RTUlSece sess... oS eee Bayer eva. <.93 
Adolf Israel 
and August Blank ... ([Ger....... Elberfeld..... 
Ey Diartz and A: Israel .,|Ger....... Elberfeld..... 
IREpeber se LuilO: Geis cides. ce a0 © Switz SH Basle dees clea 
Gs K. Jagerspacher and P. 
tt 
Krohn, Carl. See M. Hoff. 
mann. 
Kronholz, Erich. See A. 
Schmidt. 
Krenlein, Gustav. See <A. 
Schmidt. 
Wert aa Cath, ou vicn tiny ais ccd ss (Savio Beyer, Kegel. 
G. Tobias and E. Kegel ...|Ger,...... Beyer, Kegel. 
PRR, PELOEMPICE we c's a ieee ve Switz . |Hoffmann.... 
Kuchenbecker, Adolf .......... Gert a. HGchst. .2. 5/5. 
Oe We ea. Po esis eels « Weer ce i £5 Elberfeld..... 
IBavetee streets = 
Elberfeld..... 
Maveap at) and Curt Paling .|Ger.......|..cesereesees 
MUERTE PHS fo gle ws ode t'e's cx « Ger eye as Griesheim.... 
(see A. L. Laska, A. 
Zitscher and A. Winther) 
and Edwin Acker ........ AOE wok 5 eo Griesheim.... 
Chem. Found. 
BVO SIE CaS do nr CFE oaks 0 69 Badische..... 
(see R. H. Scholl) 
Basemanl, Cart 6.5. ce wk ces SiitZaces Basletiearcte s/s 
Bete Ol eR OMe os hin hos o's (GER o ate ne 3 Hbehsts.. +... 
Rvriges: Lucas Po tii eks sis: iS uh eae Gen. Chet. 
National;..... 
Mabbandtew Pitt i. oe acta ciee des ‘Cade An ae FLOCHSt ac cave a 
AbGATGt, ELAUB co n< 5-5 a.s sess Ger sa. «0's Badische..... 
Lagutt, Jan. See M. Boniger. 
Laiblin, Richard. See P. Julius. 
MM MOP tS VAT is cs ax cee | IN. Yeses Rumpff (34). 
Bourgade..... 
atiy Pile broncos) a... ccs. « Er Pray cea ates lett state total olay odie 
Lasiders, Hermann. See K. 
Schirmacher. 
Landrivon, Joanny. See J. 
Altwegg. 
Lange, Martin and T. 
FEU TILL WV AG TMM er siiNs fareclauevatsysse ¢ 9s EN etligra co nreissl aieicpecupeseeeyorerersl 3 
Lange, Otto. See A. Wein- 
berg. 
Lange, Werner (see W. Herz- 
berg, R. Kirchoff and _ J. 
POSCICH CEL eee seas © sieht tie) nie Gere eosin Begiity sy. cictel 
Lantz, Robert. See A. Wahl. 
Lapworth, Arthur ............ PUES avis afte dis ate leahd aie me 


36 


DYE 
GROUP 


vil 


XXII 
XXIII 


IX 


VII 
XXII 


XXIII 


PATENT NUMBERS 


941,152; 960,008. 


1,449,681. 
1,429,953. 
727,387. 
920,156. 
664,955. 


546,068; 546,060; 546,070; 
563,383; 563,384; 563,385; 
563,386; 613,641; 613,646. 

563,382. 

602,855; 792,600. 

602,856. 

602,858; 603,090; 603,645. 

498,982. 

518,458, 


602,857. 

603,646; 603,647; 603,648. 

805,918; Re. 12,555; 
806,415; Re. 12,556; 
807,289; 823,793; 835,539; 
844,814. 


351,056. 

es 

m) 1,316,047. 

839,605. 

729,073; 775,367; 775,368; 
775,369; 808,762. 

085,352; 994,756. 

722,719. 

(pl) 1,414,139. 

(Az) 1,169,267; 1,193,566. 


(Az) 1,127,027. 

(Az) 1,426,209. 

876,810; 992,567; 1,058,604; 
1,464,079. 

403,678. 

458,283; Re. 11,231; 
458,284; 484,521. 

458,285; 458,286; 473,467; 
511,808. 

1,345,373. 

1,478,039. 


244,757. 


891,708. 
871,600. 


82,120. 
(Ab) 109,025. 
134,076. 


702,445. 


1,408,363. 


1,431,470. 


556 DIGEST OF PATENTS 


PATENTEE ee fede ASSIGNEE vee te PATENT NUMBERS 
Laska, August (see A. Winther)|]Ger....... Griesheim.... Til 1,016,638. 
Oehler....... VI 679,974; 724,893; 724,894; 
728,477; 740,767; 740,768; 
767,069; 767,070; 787,046; 
798,808. 
Griesheim.... VI 832,393; 839,480; 849,690; 
849,739; 860,220; 860,221; 
863,290; 964,918; 964,919; 
964,920; 971,761; 971,762; 
982,507; 982,508; 982,509; 
987,999; 988,000; 995,160; 
995,161; 1,001,286; 
1,049,109; 1,094,448; 
1,206,232: 
Oehler....... XV_ | 720,874; 775,570; 785,675; 
; 801,598; 843,156. 
Griesheim....}| xv 999,045. 
Oehler......; XXII | 798,807. 
and ‘Georve [istuS os ccn bees Gere. ee 2 Griesheim....| XV_ | 841,877. 
and Hans H. C. Prillwitz .|Ger....... Griesheim.... XXII } 1,425,392; 1,425,393. 
and: Ernst: J... Roth* 0. 02..: Ger ices Griesheim.... III 1,079,568; 1,162,496. 
and Arthur Zitscher ...... Gert sy tect, Griesheim....| VI | 1,091,148; 1,121,026; 
1,145,072; 1,452,083; 
1,457,114. 
and Felix Kunert ...... Gere otes Chem. Corp...| VI | 1,042,356. 
and “Ernst, J. Roth s.. oe Ger acess Griesheim....} III | 1,042,931. 
Latten, Matthias (see A. Blank)|Ger....... Synthetic..... VI_ | 1,169,329. 
Lauber, Eduard and  Lwigi 
Caberti? S45 ea tea eee Gerri hia Bayer........ VI | 542,022. 
Laubmann, Heinrich .......... TY da Hochst 2... aa% TIT | 511,901; 555,904; 569,418; 
569,419; 648,271; 656,463; 
727,380. 
Latch? “Richardt... .ecee Geri. 3 fees Bayete tce.4 VI_ | 476,393; 479,515; 503,148; 
(see M. Ulrich) 509,623. 
Berlin ties Sse VI | 912,138. 
s Snaietmaniannne XV_ | 764,733; 764,734. 
XXIII} (Su) 764,735. 
and Mo Kahaw.. 3500.2" Geri visi Bayero seca VI _ | 440,639. 
and M. Krekeler ......... Get Bayer... cise VI 438,4387 464,775; 502,368; 
502,369. 
Latth,<Chaties fos, ako te Nig AR ae: sale Sits ooooe| Ep $96,242. 
Lawrence, Winthrop S. See L,. 
C. Daniels. 
Lawson, Thomas A. See A. G. 
Green. 
Lawton, George McC. ........ Masai..2. a alia anaes XXI_ | 763,616; 768,809. 
Teaming, Thomas H. ......... N> Ve. 22) | National=-.6. VI 1,365,040; 1,372,439. 
and Theresa M. Siisemihl .]N. Y..... |National..... VI 1,363,886. 
Lederer, Leonhard .......... Oee to ahs wit ttoneee XXTIT | 654,988. 
XXIV | (m) 543,579. 
Boehringer... | XXIV | (™)503,748. 
Legg, David A. (see C. Weiz. 
MANNF eels ctor arch Moe ee Bngsieae Adam.......-| XXIT | 1:447,557- 
Lehmann, Fritz. ...2550 aes Gertete: Bayers eter cet Xv_ | 866,939. 
Legh ul ewiste ek usher ae Wage t’. 3). bs venta oe eee XXIIT| 186,485. 
Leloit, J wlesil wie cece ace Bogiscs cs Posseltic... XXTIT| (Ab) 248,934. 
Lendle,\ August ).4 soso eae N. Y..... |Pickhardt.... | XXIII] 1,375,919; 1,378,418. 
Leonhardt,<August. $.L.5 71 a Gere el eee ee XXIII | (Tr) 49,958. 
Leopold, Richard. See K. q 
Schirmacher. 
Lepers, Piétre sy .4.00 ce ee Erste (ee ncotee pe ime XXII | 2,311,548. 7 
Lepetit, (Roberto 7)2i tee. Italy v.v5: 
and Ernesto Tagliani ..... Italy i ccke tee ee XXI | 704,843. 
Leroux; fi enti ®es hse, eh BGK aletcgaless Soc. d’Eclair. | XXII | 1,318,212. 
Leroux; Pierrt ts 260 2 ee eee Hrs ee Soc. d’Eclair. | XXII | 1,326,515. 
Lesser, Emil. See E. S. 
Chapin. 
Lesser, Rudolf nce oe Get. ates Hochst. .... <5 III | 1,009,981. 
XXII | 729,876. 
Levinstein, Herbert .......... Eing.2 s-coo desk cae eee VI_ | 1,283,231. 
and James Baddiley ...... Bag:2.i22 Levinstein....] VI | 1,052,262; 1,092,842; 
1,153,555; 1,185,413; 
1,232,056; 1,365,706. 
and Max Wyler .e.5- sen oe Hinges Levinstein....| VI 1,024,794. 
Levinsteiny fvan oo... sense ote Eng. Arse Wee eee tenes IX 289,543. 
and Herbert Levinstein ...|/Eng...... Levinstein....] XV 732,090. 
and Richard Herz ........ Engi Levinstein....| VI 619,194; 629,748; 634,009. 


XVIII! 668,580. 


PATENTEE INDEX 


DOL 


T 
PATENTEE eee ASSIGNEE ia aba PATENT NUMBERS 
and Carl Mensching ...... iat Mag oes Levinstein....| VI 622,961; 654,167; 654,168; 
eer 722,860. 
702,369. 
eT bn pt ged ete er 706,969. 
i i eee = 6 ’ > ’ . 
and Ernest E. Naef ...... Bg 6% ara XV a ie ag 
and Hermann Pfeiffer ..../Eng...... Levingthine. © VI 625,174. 
ROW PROP EE ec iais osteo ee ss ERE. os National...-- | XXII | 1,420,198; 1,429,514. 
ieee Sees ae GIpbay.. ... Es nce es U. S. Govt... | XXIT | 1,288,431; 1,293,610. 
z PAM cd sha aioee » 
ee etlentyes |. |Eat °° |Gas Coke.r..| %V | xa6s.ss 
Leykauf, Anton .............. Wpvariacs. | see eyes is XX_ | 87,270. 
Lichtenhahn, ii Gratien mere Wonzava. aca XXIT 1,311 824. 
mee era, Latwittiss...3-. Ana eling.ci toe ete aes xin: ete (Su) 960,975. 
Ser eee ce viel de cs ss ses |NOrway...|ecscseeceescd 
Liebermann, Charles. See C Sadho ae 
Li Sheds oe H. Caro. VII 
teminecht, “Oto? oes cesses. Ger.......!Roessler...... I 63,377. 
(See B. Homolka) ; Recutet ans ay (cay 847.083. 
; 903,588. 
» and) Ferdinand Blumenthal .|Ger.,.....|....06000.00- XXIIT] 1,059,740; 1,059,741. 
Liebmann, Adolf ....... Ma 
pedal Ieee aes. VORA) Poa BORE hm ata ae 404,097. 
XXIT | 374,250. 
Bas es gy BG ee ace XXIT | 252,782. 
ee ee eee at ee 7: s- | Cer... .. , | ene ce oe en «eles XXIV | (m)741,585. 
t A Geter seat 7415595 
PARC Rte, ISRO. oc. on edie seine 7 One ey ta) PEAS eo Rae III | 500,917. 
Lightipot gi Ohi: sce sevcss-s. Eng...... lessocs settee XXIIT} (1n)83,182; Re. 3,647. 
g : 31947 
Miiller-Pack. II 38,589; Re. 4,746; Re. 4,747. 
Brown....... II 111,654; Re. 7,420; 
or 7,430; Re. 7,431; 
C. 75432. 
Ed GW Oa oa Assen coo. [e sere ceeceues XXIL | 1,427,215. 
XXIIT} 834,739. 
Jiceven Geriatr .245..6.. Gere. i0% oe ) eae A 208,5055 268,506; 268,507. 
impach, Leonhard ........... Ger....... ochst....... pa AE 
MAR OESGMER WT eas Pos 6.5 iid wlvin e's’ Gere. . 5... Hochst....... XV__ | 674,137. 
pe Be a a iN. ¥ Ul trOn yn ass i oe via a oy 
tert. |Chem. Found.| XXII 1,378,882; 1,414,029; 
BeMMie tot Aa acaes fe bs 1,414,030; 1,414,031. 
List, Georg (see A. L. Laska..|Ger....... Griesheim... XV 889,936; 960,652. 
and J. Flachslaender) 
pe ge BPE ee Ss a iS ee ree ae 
oa and Victor P. Gershon ....|N. Y..... Grosvenor....| XXII | 1.458715. 
oyd, Nathaniel and John G. 
Daa ei eter ae ec uk ts ¢ 4 oe Baa Ne Feige ciascie- | ele 2 tlenaie alee XXII (Tr) 34,840. 
Poach Walther oh... oekeislce sss erties: Boehringer.. oe Tei ees 
Lohmann, Clemens ........... (ree. Pune Cais ee ee 3545714. 
Lohse, Otto. See A. Luttring- 
haus. 
Lommel, Wilhelm ............ Gere Bayer........ XI | 856,536; 856,537; 884,745; 
893,855; 902,154; 936,247; 
936,248; 961,361; 961,362; 
962,712; 985,424. 
Loomis, Chauncey C. ......... N. ¥ Semet-Solvay. on aoe 
xXXI 1,427,400. 
Doretau; Ferman ............- Switz..... Durand scs..0% XI | 844,155; 844,156. 
(see C. de la Harpe 
and C. Oswald) 
Ne ROD OS ia eos caine ss => Tenn..... foscreeeseeees XX _ | 88,793. 
Lawler VOstar Geass ssc s = Os SAE Chem. Found.| XXIV | (t)1,421,701. 
LOWE HATES ec cai ane eces Eng...... [rrrseere »...| XVI cane 316,471; 318,484; 
333,049. 
Lowy, Alexander ............ Parner sce 
and Arthur H. Howald ...|Pa........[eecerrerteeee XXII | 1,449,423. 
Lubs, Herbert A. See J. A. Am- 
bler. 
DGder. Birhard «oscars. +s Geren sas ha hte att aes 
OCHStae ene oi m) 1,230,185. 
Liittringhaus, Arthur (see J. 
Abel and M. Isler) ...... ET es eae Badische..... III | 1,002,066; 1,010,930; 
1,011,068; 1,196,127. 
XV ; ie, 779800, 
XXII n)968,376. 
and Louis Blangey ....... Getic hose Badische..... XXTV | (t)1,412,949. 
and Wilhelm Braren ..... Geriatr Badischew..a' Iit 1,035,023; 1,067,046. 


558 


DIGEST OF PATENTS 


PATENTEE pease pe! ASSIGNEE ans. PATENT NUMBERS 
. iesbach 
Dey eae areas ie era Gere... Badische..... III 1,018,836; 1,018,837; 
1,044,673. 
Vi 1,083,110. 
and Ludwig Ejifflaender ...|Ger....... Badische..... XXII | 1,394,851. 
hs 
Roca acct Sapper ..... (Boh daceeateanes Badische..... III 1,090,636. 
and Ernst Schwarz ....... Get oaks Badische....°. III | 1,044,674; 1,044,675. 
DAtratip aD rmestOseniene eos PXSA5 i oF TTS Gell wats teeta aeevers XXIII} (In) 700,521. 
Luther, August. See C 
Millers ieee cdeie ne oie aie creme 
Maag Rudolf on svccpia cielo Ceres 2. Tschat. out sae III 1,015,329; 1,018,433; 
XI Cay a 
and Pant fore cccnesen eee ee sae esis Héchst....... 1,065,063. 
McCallum, Nat 2 APOE RY ee tord Th a tay ee ae Leeds: 2.,.55 XXIII | (Nt) 283,265. 
McCann, Robert B. See D. aot 
Cuttrown. 
McCormack, Harry ........... RUS edn Shee ee Pe XXII | 1,406,745. 
McCreadie, John. See M. E. 
Putnam. 
McDonald, “Edith OQ... 55.0 4 NevYoo sei (iis ce ea een XXI | 1,222,433. 
MeDonald, David Bu «.2.... 2. lg a pc oss ht edie Werte ae ene IX 1,396,001. 
and Jackson Calvert ...... Eng....-- McDonald....| xx vy | (e)1,320,076 1,320,077. 
MeEirdy, Sarl: Po opens ee D. C..... |Chem. Dev... | xx1r | 1,205,339; 1,308,796; 
1,315,220. 
Machenhauer, Fritz ..,...... She ECHUS Naet tr ceibnlie eles aie se nsrstnteuate XVIII | 308,912. 
McKee, PRION Be en cee oe INE oh) ase atoberen| erie havabenatetereenare XXII | 15312,127; 1,449,121. 
and Herman C. Cooper .. |N, Tears MeR Geis 5 osix XXII | 1,458,491. 
Maeder, Horst. See O. Wolfes. 
Maennchen, Fritz. See K. 
Thiess. 
Mahier William + 24.0 4. 2 ciak te NG Ee eho haca oe tee XXII | 1,405,732. 
ne Gerald H. See M. Phil- 
ips. 
Majert, Wilhelm \....t., ..4<3.; Geri iss dich ited aeeans VI_ | 440,953. = 
Ewer-Pick XVI | 323,514. 
XXIV | (m)543,214; 603,195. 
Mannsgep-Orte ce eee cre) Cer. 3) 35 Bayer cides XXII | 526,786. 
Mandt, Max and Robert Hold 
MANM veces see cecsaseceses Geri lie pine eetae wees XXII | 650,332. 
Mankiewicz, Otto, Julius Alt- 
schul and Wilhelm Urban ../Ger....... Berlin ii. cies XXIV | (m) 860,636. 
Mann, Friedrich = 30 o..0 2... cea. Noy Schoellkopf XVIII | 262,680. 
Mann, Heltirich vNe vex ek cca rey cen en UE PAN es Re ie 2 XXIII | (Ab)779,228. 
Mansfield, ‘Hans Ou8) Giuaneees Getohiad.. Badische..... XI | 1,028,045. 
Manss, Walter Ad 24 Goren cee Dae: du -Pont.sec “RV Ob tar 854: 
Marchand, Robert <<...2... Nethh.t foeteu cae eee XXIV | (m)1,408,462; 1,411,859. 
Marchlewski, Leon (See W. H. 
Ciansp yh oho key c eee os (Pesca. se 
Edgar S. Wilson 
and ‘Ebenezer ‘Stewart ..|#ng,..... [2 +405 s04950 0s XXII | 633,245. 
Marckwald)):Leor: Ssh. os Ger....ccclossccccercees XXIII | 721,961. 
Marshall) Johns arn bake Paveey fered du Pont..... XXII | 1,300,580. 
XXIV | (e) 1,326,047. 
Marshall, Melville J. ......... 
and George S. Shaw ...... @ar wees: Shawinigan XXII | 1,450,982. 
Martinon, Barthelemy. See C. 
Savigny. 
Martius, Carl A.tgsey seine ace | Pe an apes a anes BUTS Bee: VI 268,113; Re. 10,3535 
344,971; 358,865; 456,897. 
Bronnert ica: VI 1 334,257. 
Berlinnaecawr vI 456,627; 456,628. 
stun taro tetaterstolonets XVI | 246,327. 
Martz, Edward. See K. Krek- 
eler and C. Heidenreich 
Marvin, Joseph B. Jr. ........ INA Ying SSeS Oe aor terete XXII | 1,442,401. 
Marx, Karl. (See A. Erlenbach)|Ger....... Berhws os0 55 II 1,105,447. 
XXIIT] (Ab) 1,183,748. 
Mathe, Eetnest i, foo) 6 hee Gertiaeies's Hochstuaeassase XV 763,193. 
Matheson, Howard W. 
and George E. Grattan ..../Can....... Shawinigan XXII | 1,425,500. 
Mathieu,» Jeam Avmoy tone ace BA win a) eA een Mes XXI_ | 356,368. 
Maupai, Kugene I5°. ons. cee Teac Sure here ade stems XXIII! 1,352,014. 


PATENTEE INDEX 559 


COUNTRY 
OR STATE 


PATENTEE ASSIGNEE | Group PATENT NUMBERS 


Mayer, Bertram. (See B. Wuth, 


A. Schaarschmidt and F. PAW IE Ze ac are Hh ESASLG gg wc a oe x III | 1,097,343. 
PR eahety) Me nteicare cue iact 6 ewes <s 
and Adolf Pfannenstiel ...|Switz..... Basie so. cees XV_ | 927,868. 
and Alfred oS aaa .|Switz..... |Basle........ III |902,895; 915,385. 
anid Veopold Weil ........ DWiCZ iene + of DaSk Gere cone crs III | 1,044,797. 
Mayer, Carl A. (See J. Mohler) |Switz..... |Durand...... XI | 440,359. 
and Charles de la Harpe ..|Switz..... |Durand...... Al | $47;173.- 
Mayer, Rudolf. See W. Bauer . 
Mav wald, Mnedericic. Jc si... 6s s PES Us 3: XXI | 894,065. 
PLOCKEDACH VEVINSt. 6 ccc esas Crete ae oes Baverni sk 30% XXIII | (An)970,072; 970,073. 
Synthetic..... XXIII | (An) 1,203,642. 
Meincke, Alfred M. .......... Mtar Wie. a abate bake e cis « XXIII | 276,061. 
Meisenberg, Kurt. See W. 
Schulemann. 
Meiser, George W. See R. 
Knietsch. 
Meiser, Wilhelm. See C. Bosch. 
Meldola, Raphael ............. PGLU a 5 ces Leaps 4 se ae 800.5 XVIII | 263,420. 
Net tee (CHIU 5 Be Oe ee eee bey es Mounsey..... VI 1,217,042. 


(See H. Vollbrecht 
and I. Levinstein) 


Dlentua Pugene css. cesses Gera. .ss* Badische..... XXII | 449,551. 
Merling, 2 OO Get.. fsase Hochst....... XXII | 691,157. 
: XXIV | (£)714,931. 
and Robert Welde ........ Ger.....<. Hochst....... XXIV | (£)743,305. 
Mesel, Guido. See A. C. Bur- 
rage, Jr. r ; 
INESERLET W CDATICS. coc cs woe s.s 00 Switz..... GOIEY fea es a's VI 1,157,169. 


Metzger, Richard. See O. Bally. 
mi hero Alexander. See A. 
Green. 
DOr OC ie koa ase est esnes Ger....... Bayer........ VI_ | 888,522. 


XI_ | 499,243. 
XIII | 890,588. 
Meyer, Felix. See H. Gelder- 
.mann. 


Dover, FACOD caceccssccsse oe Ger...... .|Bayer........ XXIV | (m)533,718. 
reer tt Te ces cnc soe sa eee Get cases 
and Friedrich Berguis ....|Ger......-]sereeeeeeeee A AIL, }4,0625357. 
Sewer PSU Te). G yeu wse cee see OS ee eer ‘beeee VII | 310,604. 
Meyer< Robert ........0...5. 1 ote ane ae Poulenc...... XXII | 1,410,494. 
pe as Ernst and Carl Hen- 
ioe Se OG SE Ce ee eer eee eer; reyegene 
Michea, SSO Es aS a arena Can. Is... [eseee se eeeeee n) 388,703. 
Midgley, Thomas Jr. ......... Ohio... 3: Gen. Motors..| XXII | 1,467,905. 
UIE WBMP fons ccc aces Geri... Bayern eit se III | 960,182; 996,109. 
(see P. Thomaschewski) 
pPiverech, Walther Fi. ccc cc ces. Ger......e|erese te eeeees XXII | 889,799. 
Miescher, Karl ........0..000: Switz..... |Basle........ XXIV | (m) 1,434,306. 
Milarch, Ernst. See F. Singer. 
Ser Bo re N. Y.....|Grosvenor....| XXII | 1-445,637. 
Miller, Stuart Py ......5..00:- ta Ree Barrett.. ....: XXIV | (PI) 1,360,665; 1,395,068. 
ang youn mh: tess .......:. Lt Barrett......- XXII | 1,457,543. 
and Frederick H. Rhodes .|Pa........ Barrett... 2... ; XXII | 1:438,710; 1,451,666. 
ae (pl) 1,365,423. 
Miller, WV AlGET ie css. font thcsie ais Ek ehs eal ROla Oct uC oe 1,359,45 
Mitscherling, Waldemar O. ....|/Del....... Atlant. cae. XXII | 15452,520. 
Mittasch, Alwin. See K. Ner- 
esheimer and C. Beach 
Mbtiegiok. Carl on c.i senses (Senees cscs Bayer. «oss ..| IIL | 1,036,880; 1,036,881. 
invoice WES 225 Ba eee emir Ser 2. cook Betlinvto ae: VI_ |509,920; 521,985; 521,986; 
(See T. Diehl) 539,699. 
XXII | 511,708. 
and Carl Oelschlaegel ..../Ger....... Berlin... iss VI |543,747; 543,748. 
IOCHeTE NVI, care Neda y dance ss (eee heey: Chem. Found. | XXIV | (t)1,399,510. 
NL GCSE LATCIN | fo iie eis s.e:0 le ors ase ese Eta Hochsté.. cc.> XXII | 729,502; 757,136. 
Hans Hertlein 
and Ehrich Oppermann .|Ger....... Héchst....... XXII | 742,707. 
REDCAR UATISIR vg StS sf ax'ce aes Tadein oe (ates cc a.cs XXIII | 1,066,641. 
Moffatt, Miles R. and H. S. 
STEER AIR ae 1A) Ben oeeen Roese pun cicmice XV /|886,532. 
Mogenburg, Julius .......... Geras cece Ravyeriess. ses XXII | 953,049. 
Mohler, Johannes (see _ J. 
DUE cia fos enka sn eats s 3 SCilds sie cia] eaShe regen « oe XI | 420,164. 
and Carl A. Mayer ...... Switzs.s.. Durand XI | 444,538; 451,502. 


Molineux, Edward Ll. ........ IN Ve ae INE es, rene retare peers XX: | 76,935. 


560 


DIGEST OF PATENTS 


PATENTEE pei ASSIGNEE att he PATENT NUMBERS 
Molt iGustavaivur ciatele saiclecers cists Mass dik rit cpoca citer nies XXIII} (1n)179,939; 220,638. 
Moness, Jacob M. .........+-. N. etic lishosshenerer natin ooh VIL | 1,308,763. 
Monnet, (Prosper “Pierre 7 0. i.3 | Fro 2... 0 Soc. Chim II 298,998; 387,097. 
XIX | 499,927. 
XXII | 606,470; 613,460. 
ais ewes «we XXIV | (£)548,719; 551,131. 
Monroe, Kenneth P. ........ Seas RNY Ge one wciena gE merece XXII | 1,357,467. 
Montgomery, Samuel A. See E. 
H. Payne. 
Montmollin, Guillaume de. See 
de Montmollin. 
Moore, Wy ont (Soo. orks eee Pee a ile lots aa oe cece eee XXII | 1,358,324. 
Moran, Robert Co .ccs coe FY at Gaia ie dt Pont, ..% +s XXIV | (e) 1,401,631. 
Morgan,, Gilbert (1. (o.ee. .. Bag iocw st decree rere XXII | 1,273,901. 
Imp. Trust... | XXII 1,442,818. 
Mids Jalevoae Sy sedbinwsocnad Massey ee xis Chem. Prod.. | XXIII} 854,374. 
Moss, George wANieea aes N. Ha NARA ieee aeatet he sac a ae 64,897. 
Mott, Owen. See A. E. Holley. 
Muchall, ‘Theodor? aeccscs ees Clueletcels Kalle ae ur ee XV_ | 796,443. 
Miller, Armand. See M. E. 
Waldstein. 
Muller f:Carloc. hic cae bine as ve Leee’, cies eas Kalle. = sas VI 1,113,468. 
Badische. i: XVIII} 501,434. 
and Max H. Isler ........ Geriyen ate Badische.o. so NOE 1,062,988. 
and Wilhelm Stober .... |Ger....... Bagisthew-ae: Vi 1,168,531. 
Miiller, Carl Ludwig irene tal pe Caer Ger ensnecee Badische dinene I 546,177; 746,981. 
(See A. Kern and H. Bull) VI 430,533; 430,534; 430,535; 
524,261; 524,262. 
‘ XVIIT | 353,264; 353,265; 353,266. 
anG A rtist, Schinid .. 10s ee Ger......- Badische..... I 716,264. 
Moller, Carl: Os@ar ud. sees SwitZs..0~ aslev cnet. VI 524,060; 524,070. 
Durand jo... VI 628,721; 631,089; 640,010. 
Frochstiraeryor VI 941,088 
Bindschedler..| XIX | 576,222; 576,223; 578,578; 
84,119; 596,333. 
Badische..... XIX Paar 82 
and August Luther ....... GPs see Hochst... 22.0 VI 1,041,146; 1,069,950. 
and Alexander Otto ...... Ger......- El6chsts. ase VI 888,837. 
Maller. Bamihis ort ea cock ok ok Switz Hoffmann XXIV | (m) 1,352,082. 
Muller “Hermans sa cekisicis eiels Lives ions wis eer'|epetntovele tevorene tate XXITIT | (In) 808,308. 
Miiller, Jean J. See IL. Jaros- 
son, 
Mueller:stigcar! © 2coee ee ose Noes Schoellkopf VI_ | 688,478. 
Miller, Rudolf (see A. 
SCHMIGC) 27 Ca. oe roeer Ree OS Brant cane, Hochstiensese XXII | 804,157. 
and Otto Schwab ......... Ger...... «| Hochst.) ..%s XXIII | (In)723,007. 
and Waldemar Wollenberg.|Ger......- Hochst). 2056 XXII | 841,990. 
Miiller-Jacobs, Armand ....... No Y..4 > Miller-Jacobs.| XXIII | 342,207. 
Russia Burtnettee aes XXIII | (An)243,378; 245,633. 
Miller-Pack, Jean J. See LI, 
Jarosson. 
Monch) “hduard yes spel ree, Gér.c sss. Badische, <u. VI | 737,445. 
(See P. Julius) 
VII | 910,830; 943,560; 943,561; 
949,592; 1,122,790. 
; XXIT | 1,003,280. 
Mugdan, Martin and Willy Her- 
MANNE oc weet ane ee 2H GOL. saves Cons. Elek.. VII | 960,671. 
Mahlert, | Franz; s,s seas Aus.-Hng..|Kinzlberger.. VI. | 528,065. 
Murphy, Waiter Bo... ).2 Pa.....e 
and Wilbur G. Dunning ..|Pa........ Barrett, oy). oi XXIT | 1,400,897. 
Myers.) Chester” Ni eee N. Yiuwses Net? Sateen XXIV | (m) 1,422,294. 
Mylins, Adelbert ............. Switz..... Geigy 08s. coe VI | 376,392. 
Mylius, Albert. See C. Ris. 
Naef, Ernest E. See I. Levin- 
stein, 
Nagai, Wilhelm Nagayoshi ....|Japan Bunnelli..,.. XXIV | (m) 1,356,877; 1,399,144; 
1,300,312. 
Nagashima, Hajime ........42 Japan Tainan Seito. | XV sonia 
Nastvorel: Oséar 24) Seo o0 2s Ger....... Elberfeld..... I 675,568; 716,084. 
Bayercnn ewes XVIII | 496,435. 
Elberfeld..... XVIII | 605,119; 658,504. 
XIX | 738,227. 
and Friedrich Reingruber .|Ger....... Bayére sac XVIII | 517,473. 
Wath es yout scene eee eaten (SEL. tia Hochstieey ee Til 4763; 103. 
Nawiasky, Paul. (see R. Bohn,|Ger....... Badische..... III 1,062,990. 
P. Julius, P. E. Oberreit and XXII | 1,238,932. 


M. Kardos.) 


PATENTEE INDEX 561 


PATENTEE ReIAEE ASSIGNEE fied tll PATENT NUMBERS 
Neelmeier, Wilhelm (see H. 

Jordan ‘and J. Jansen) ..... Gerirenn, Bayer gees s 405 XXII | 994.420; Re. 13,304. 
and August Sigwart ...... (EY S deena Synthetic..... VI 1,128,813; 1,128,814. 
Heinrich Jordan and 

eatitledaner: >.> J... (ORs). ose Synthetic..... VI | 1,169,344. 
Nelson, Hinathan-K.°.......... Didoes sss < U. S. Govt... | xxtv | (£) 1,329,272. 
INcISON a alnneA ees tis as os b NEN ates a td National..... XXIL | 1,469,586. 
ORGHCIR MEOTCOL Vege. ciceee sss Switz... |Badische..,.. III | 443,402. 
Neresheimer, Heinrich ....:... Gerinnass .|Badische..... Ill 1,052,507; 1,207,981; 

1,207,982. 
Neresheimer, Karl, Karl Bosch 
and Alwin Mittasch ...... Gerke oe 2. Badisches. 5... XXII | 1,274,503; 1,292,019. 
Preumant, 9 Max soto Cette sits Westfalisch...| " Tx 666,627. 
Neville, Sylvester M. ........ CE hk f Lee Lohr Bake XX | 396,417. 
Newsome, Thomas ............ Bas. 5 os Amer. By-...-| xxqz | 683,786. 
Nicodemus, Otto. See A. Stock. 
Niessen, D. See G. Kalischer. } ¢ 
INTEtZKT OR UGO ir atcshoae cess sas Switz acs tae Hochstam mie VI 424,019; 555,658. 
Niewwiand, Julius A. ......... Pie ere ot Pure alee et eal o-0”« Il 1,326,367. 
Nightingale, Donald A. See W. 
Bader. 
Nissen, Detlev and Erich Saul .|Ger....... Cassella...... Tt | 1:055,287. 
Nomura, Hirochii.c..25...... JAPAN ree [eve descr cnaus XXL | 130,710. 
Novotny, Emil E. and D. S. 

J STG ENN 0 1p ee ae ee a ae N. J see eee Stokes shies) ele a ¢ XXIV (pl) 1,398,146. 
Woroy, Charlies F.X.......... Rar eere ano oye || Cremetn sien reenact XXI_ | 493-286. 
Nydegger, Otto and H. Schel- A. 

ee ae WIZ. 2222 |e ceenesenecee XXIL | 19417:277. 

Oakes, Francis J. ............ BREN de oh ce pie ese vn 5 5 XXI | 759,008; 872,250. 
Chere Paul Ts... ccs... Ger....... Badische..... VIL | 739,148; 731,385; 761,007. 

(See R. Knietsch) XXIII (In)765, 590; 835,462; 

Victor Villiger ; 999,055. 
and Paul Nawiasky ...... Geter rss Badische..... VII 948,241. 

CEI SDM tC. er SWE css, 1) POSE in oo ve XXII | 14455544. 
CoB Uiit, IRATE ON. Sakis des cesses LS aa age oe ea VXTV (m) 1,299,214; 1,299,215. 
Oehrn, Hans. See O. Kaltwas- 
ser. 
Oelschlagel, Carl (see M. Moel- 
Ee he Be ae ec) Se ae AZOT, oo eg Betlin’-.32'.3 VI 628,025. 
Oppermann, Erich (see M. 
DGOME Ds rad ord se Psa op veces CREE nies Via] F918 4 824 © ce ws XXII | 823,435. 
Oppermann, Julius (see K. El- 

Belang — Fischer) ........ Gergee. s. 

and August Fette ......... 2 eee Peall@ eae oe <s VII | 673,887. 
Ossenbeck, Anton (see M. 

Kahn, O. Dressel, B. Hey- 

mann and R. Kothe) ........ Gere ots es 
aiacartnir Zart .......... Meiners ss 3 Dever iee® ares VI 1,027,148. 

Oster, Heinrich (see W. Herz- ; 

berg and H. Geldermann) ..|Ger....... Beslin wt. os.< VI 949,633. 
Ostermann, Leopold .......... RrBi less lls oa cen ne uses XXII | 1,099,761. 

XXIV | Gm)906,918. 
Ostermann, Fugen ............ Gere seis ty eres ay XXII | 332,358. 
Osthelder, Franz. See P. Julius. 
Ostrogovich, Adriano ........ Rumania.. 
and iheophile Silvermann .|Ger.......|2-0-ssesscees V 900,302. 

Oswald, Charles, Herman Lore- 

tan. 

and Charles de la Harpe . |Switz.....|Durand...... XI | 807,181; 807,182, 
Oswald, Karl. See C. de la 
Harpe. 
Le an Greteg fe), wh atst eee a XXIV | (€) 1,390,378. 
RA BAD oe ne Sek ww ko aw (ORF cisicials Bayerncs:.4 es V 940,354. 
VI_ | 423,569; 498,404; 408,405. 
and Thilo Kroeber ....... Geneve: Elberfeld..... Vv eee 693,013; 606,295. 
Adolf Israel and R. Kothe .|Ger......- Elberfeld..... VI ae 
and Franz Volger ....... Getoaa. wes Elberfeld..... vI 1507. 
Otto, Alexan . O. Miul- 
Pe er Hichst....... XXIII | (Az)795,058. 
veriach, Martin 3.00. .3...0. Ger r ees es Hochst jee cy « XXIV | (m)768,398. 
Pe OE aa ss ss 5k hni (SOR ee dacs Rallers aca. XXIV | (m) 428,286. 
Paganini, Robert (see TRS WIkR: oatels [ARLE eps c ws vI 534,573- 

Schmid). 

Soe CS IMECHE Vy aes | atereteehonereterncres XXIV | (m)710,005; 717,016. 


Ae eS AIMIUICL six be sig tise 0s Conn. . 5. .)U pee Govt...) ccd haar Oy ae 


562 


DIGEST OF PATENTS 


PATENTEE Se ecre ASSIGNEE real PATENT NUMBERS 
Paral, wAlired cass a sees aes WEASEL. anid vl wine poeeb ie a5. XXIII wee 63,084. 
N)74,935; 93,900. 
Gerson....... XXIII} (An)86,939. 
Renwick..... XXIIT} (An)95,039; 110,094; 
Pathe, Karl (see A. Israel) .. |Ger....... 113,918; 113,919. 
and Oscar Dressel ....... Get. c nace Bayer. sy caews VI | 532,479; Re. 11,491. 
Pail Ludwig 5 sos eww eae sane ASQ acapate eS bis Wek oe ae VI 380,402; 380,403. 
Pauling, Curt. See K. Kulas. 
Paulus, Herman W. ........:; ING: Lis Royals vsse ss XXITL | 1,445,162. 
Payman, Joseph B. See J. Bad- 
- diley. EI e 4 
ayne, Elmer H. an 
z and Samuel A. Montgomery|Ill........|Standard..... XXII | 1,453,766. 
Peachey, Stanley J. ..........- BONG ony on. d Wate wr aiese pew XXIV | (pl) 1,443,381. 
Peacock, David H. See D. Se- 
galler. 
Pearson; ErankP.ace aoe WE RES. ease Arnold... 2a XXUI (Ab) 491,951. 
Pennington; John C037 0o. +. Ne Jevennt be wesc sas singe XXIII (Tr) 385,426. 
Perkin, Arthur G. ........0.- Hage dons British Dyes..} XXII | 7 345/972. 
Perckinys Walliain Eeaneee ss cient Bagi ier feed bavinagsuietns een 127,426. 
Perruche,: Lucien J.J... scans Eels esate cece ee eeee XXII (e) 1,325,168. 
Peterhauser,) Frits’ cate. c. Refi e os Hochst....... a (In) 710,800. 
Peters; Girstay i aa te nes hak Geri. cee efeceseeeceeeee XX | 1455-448. 
Peters, William A: Jteiss.isass Del....... du Pont..... VI 1,466,411. 
Petersen, Ferdinand ......... Switz..... Petersen..... XXI 578,580. 
Petérson, Oscar: £0... ent Cont... 2+ [ecnwerensnces XXIII 1,386,201. 
Pfanner, Frederick ........... R. Tow. e ee deer eee eee weee (An) 4,192. 
Pfannenstiel, Adolf. See B. 
Mayer. 
Pfeiffer, Hermann. See I. Lev- 
instein. 
Plenniges, Anton). eo 02006 bs Switz Brugg.......- ay 698,220. 
Pfitzinger, William .......... Gee as Bayer........ 428,629; 501,160. 
XVII | 406,952; 446,009. 
Pieger,  Tohaines. acs 1024. , Get awe cen Roessler...... VIL | 680,395. 
Philipp, Curt. . R. Seifert. , 
Philips, Alfre ree mttaanea Geran: ace pe vi oece Behe 
and Moritz i Pi gost Ochst....... bade aba ie 
Philliges Mae Gi Ta tWinke U. S. Govt... | EXTY | (m) 1,332,680; 1,432,298. 
“ oe Gerald H. Mains ee Mich. ..... U. S. Govt.. (pl) 1,441,598. 
ickhardt, Wilhelm 
- and Hetmann’ Faddmeon ©. tN ¥ occ aa eae ee XXIV | (m)254,098. 
seed OReERI CEE J. Ss. eae Meee re te XXIII| (Ab) 106,616; 127,102. 
Plauson, Hermann .........../|Ger....--- Rotimatiy. <0 XXIV (pl) 1,397,144; 1,408,826; 
1,415,406. 
Playne, Alexander Witenes Eng a oes a a eae de XXIII (In)715,213. 
Pocius, Raphael ..:i...10.0, Bi BG reer Gen Ties ce wat corres 
Poirrier, Alcide F. y Liars fai winie | p Oe Bre wie 2 iene 0 hie nates 
Miah ee ee XV. [56%:9783 04002 ae 
5,547- 
St. Denis.... | XV | 532,484; 561,277; 708,662; 
740,465; 763,320; 904,224. 
Lieu ae ered XVIII | 423,341. 
ee (Su) 646,760. 
‘ Sate AWE Uta a gatos Vid Sea Sh greats eal ce V 502,912. 
and Daniel A. Rosenstiehl .|Fr.. Boke VI a8eean 
XXIII | (Tr) 297,844. 
and Zacharie Roussin ..... bf ee ee cee a steees VI | 211,525; 211,671. 
St. Denis.... VI 380,928. 3 
and D..A. Rosenstieh! ..) Fri... .000|ooese cece cere VI | 211,180. 
Pokorny, Joseph. See A. Fisch- 
esser, 
Polikier, -Fleinrith chao. cee 2. Clerc.) se. Berling<. s+ VI 1,003,293. 
XVIII | 680,732; 684,457; 688,966; 
688,967. 
Pollaken Fritz chester Ais. cet os Chem. Found.}| XXIV (pl) 1,369,352. 
Popen William Grr acsttorse een Mosc viitetnlinereconte oiaatareters xX 738,481. 
Pape, Walliams 800% sures aati es Erneeee.> Scottish Dyes III 1,451,270. 
Portheim, Emil. See von-~Port- 
heim. 
Potter) |) Ralph iS. yes eee Fal Paaet Fea arta Bene aps odie had | VII | 1,322,052. 
(see C. R. Downs, IL. Weis- 
berg and J. M. Weiss) 
Pratt, ,Lester "Ay sandy Fi Nt 
Briain sa habs Cee oem ts Mass....../Merrimac.... | XXII | 1,311,090. 


: 
| 


PATENTEE INDEX 563 


PATENTEE Se nee ASSIGNEE foes PATENT NUMBERS 
Preiswerk, Ernst ......0060... Switz..... |Hoffmann....| XXIV | (m)1,415,700. 
Pretzell, Carl. See K. Schirma- 
ener, OO.” Kenst’ cand A. 
Schmidt. : 
Preuss, Ludwig. See P. Seidel. 
Priebs, Bernhard (see P. Fried- 
lander, and C. Rudolph) ..../Ger....... ; 
and Oskar Kaltwasser ....|Ger....... Berlinw...... XV_ | 628,607; 628,608; 628,609; 
642,256; 655,059. 
repens he H. C. See A. 
L. Laska. 7 
Perancee ONION vice vce ecces ir semersee Soc. Chim.... | XXIII | 1,366,023. 
Pere ECO ues it cele sc iene «0 0's Catia eer Bronner..... VI 332,829; 332,830. 
Pumimerer, Rudolf ...........- GEN ayccvaies 6 Badische..... VII | 876,839. 
igiibac! G2 £0.) oe ee ea IN Wineries Robeson....: | XXI | 1,185,605; 1,283,296. 
Putnam, Mark E. and John Mc-| 
eNRET, cicul Sek owas nes Mich...... DOW cilce os ess XXIV | (m)1.459,900. 
Rademacher, Ferdinand ....... Bus sliny cece eas sone XXII | 935,815. 
Raeder, Heinrich ............. Gef...ese DAyeren suka a’ TII_ |-950,343; 950,344. 
(see P. Thomaschewski) 
Rahtien, Arnold aanccscvsresoes GOL, vniss Devens gees as ys VII | 720,217; 984,442. 
and Carl Stephan ......... Ger......- Rahtjen-..... VIL | 850,444; 937,194. 
Raiziss, George W. See J. F. ; 
Schamberg. ; 
Ralph, Walter M. (see C. G.|N. Y....- National..... VI 1,371,979; Re. 15,182. 
oe a ae ae N. Y....- National..... VI | 1,415,704. 
and Lawrence H. Flett ...|Mich......]............. IT 787,221. 
Ramage, Alexander S. ........ Eng....-- Bostaph...... XXIT 1,365,849; 1,430,585. 
Gere acne see eee ee seen XXII 1,010,377. 
Raschig, Friedrich ............ Ger......- Raschig...... XXIE | 1,023,758. 
and Max Kébner ........ CTE ire id LOS Re i ena XXII | 655,117; 656,263. 
OS Uy 2 a ae 
Rath, Ernst J. See A. L. Laska i 
and A. Zitscher. ; 
Rauch, Gabriel. See C. Vernet.|Switz...-- |Basle........ vI sahbah d salar ata 
iS eae CARRIER REE 1,335,397; 1,447,405. 
Bebey, beni Switz. asleee as ys XXIV | (p)1,316,804. iA 
as rake Josef Siegwart tai 
edman, Lawrence V., rchie 
Weith and Frank P. Brock Hy eg. ee Redmanol.... XXIV (pl) 1,310,087; 1,310,088; 
Ree anys) c rs 1,345,694; 1,374,526. 
ee, Alfred. See W. H. Claus. = 
ae mine Jah or Ae ae earn MasS...++.]-..-seceeeeee XXIII | 50,495; 54,957. 
;. Iter. P. ius. Z 
Rehiander, Paul af a Oe ie Ger....... Chem. Fab... | XXIV | (p)922,040. 
Reid, John T. and Henry Thorp|Eng..-.-- |.+.-+-+2--0-- XXIIT| (An)612,274; 631,906. 
Reid, Peter and John Eastwood.|N- J.----- Celluloid..... XXIII | 256,506. 
Reindel, Hans (see P. Julius) .|Get------- Badische..... VI | 1,126,656. 
Reingruber, Friedrich. See R. ‘< 
ae He Nastvogel and A. 
ansdorfer. 3 
Reinhardt, Heinrich .......... Ger....... Kalle........ XXIV | (m) 1,076,840. 
Reinhardt, Otto and J. Hoerlein Ger....... Weiler....... XV 1,026,881. 
Reinhold, Christoph .......... Geri es telinte ee eb leseees XXII | 868,008. 
Reinicke, Gustav ............. Gere reavas Berliticnm oer. XXII | 1,016,092. 
Reinking, Karl (see H. S. A. 
no a |Ger....... 4 
and Armand J. Stiegelmann Ger.....+- Badische..... XXIII} (In)1,106,970. 
Reisenegger, Hermann ........ Ger.....+- Hochst....... Ii 450,037. 
pens Sa gd ey Sete Gerincs selon. bee nceeee XXIV | (m)801,158. 
Pete OU BEOOUE Wit ruc ys a d+ © Ger.....-- Badische..... XI 431,541. 
Bg OOF Felon adihe...cc1 AV | Gostes 
ter, Bapti : Z 
ee Ier......- Héchst....... XXIV | (m)674,686; 674,687; 
680,278. 
Rey, Hermann. See J. Schmid. 
Reyher, Rudolf wpe SiR Ger......- Bayer......+- Vv 543,894; 557,022; 559,062; 
559,003. 
Griesheim.... VI 1,084,363. 
Rhodehamel, Harley W. ...... Ind....... Lilly.......- XXIV | (m) 1,306,439. 
Rhodes, Frederick H. See Stu- 
Diicaeh iiss Set A. Schooid 
odius, Otto. See A. Schmidt. Net 
Mere) GS osc tose oe nels ws CRO fis wae pig seg alnacein o3 XXII (In) 803,855. 
ICREICh 6 akg twice Wie Se o's s we el rai vo aihl aceie Rtietaw inate XXII } 1,322,054. 


504 DIGEST OF PATENTS 


PATENTEE Seppe.” ASSIGNEE ae PATENT NUMBERS 
eg ae ee ea ey 
i Re Seva ee Switz. )..u | GARY Sy oss.ca ss VI 991,750; 993,549; 1,067,881. 
Richard, Bernhar XX eee : : 
Richardson, William B. ....... by Pan be eae Re ae CANE ne 1,412,707. 
Richter, Gedéon ike hace AUIS ELT gon | eieiatere toy ereiera yore XXIV | (m)1,058,904. 
Ries. George SBrvak ss cn teess vas TNR Cae onde Cae ees XXIII | 1,318,100. 
Riethof, Pratz... sc sseewe aes Aus.-Hng..|Blumberg.... | XXII | 1,006,793. 
Ris; Christopher ....0%..4 6.6 -w's SWECZ, caae Geigy. ..s..0 vI 548,460; 567,413; 571,933} 
575,904}; 599,532; 619,5033 
644,462. 


XIV | 455,952; 601,063; 601,066; 
613,911; 636,065. 

XV_ | 636,066; 645,738; mart 
696,751; 698,555; 821,378. 

XVIT | 440,281. ; ; i‘ 


and Ernst Haager ........ Geri aan. Jager........ vi 888,036. 
and Albert Mylius ........ Switz..... Geigy........ I 740,468. 
” : XV 722,630. 
and Charles Simon ...... A lets Sere Geigy sass VI_ | 556,164; 615,497; 655,013. 
Rispler, Alfred L. ......0..005 Mo. -.sio0s Monsanto.... | XIX | 1,381,503. 
Ritsertwtdnardvera: eceret males CSTE 5.6 cis bos tee e eens XXIV | (m)748,101. ; 
and Wilhelm Epstein ..... Ger....... Héchst....... XXIV | (m)761,998. 
Rittman, Walter Fo... 0.3.2.< 0. Pa........ Syn. Hydro.. | XXII 1,419,124. 
Robertson, George. See F. W. 
momen bs Ney XV 6,742 
obeson, Jaco pe loa tah tes en A pdioric ode fre tte e eee eee 1,310,742. 
Spires Lote Veeears otk. N. Y..... |Ellis-Foster.. | XXIV | (pl) 1,416,062. 
Robinson, Thomas S. ......... NN Gas J een eels Sate XX | 181,282. 
Rodebush, Worth H. ......... Md... ic wus U. S. Ind. Alc. | XXII | 1,430,324. 


Rodionow, W. See A. Blank. 

Roehling. Hermann. See E. H. 
Zollinger. 

Roemer, Fritz. See E. Hepp. 

Rogers, Donald G. and H. T. 


HIOWEUIEC dd. ca se vee oh ae ns PING) Seca: National..... Lee 1,478,061. 
Rogers, “Homericns coos cee 2a LDL. ewe es du Pontes .o: XXII 1,314,538; 1,413,494. 
Rohde, Albert. See P. Haupt- 

mann. 
Robner, Josep yey? yc ows Switz..... Basie: sess VI 365,400. 
Romer; Adolph 45.05.00 esa cs Gerace: Badieches.. y, VI __ | 350,576. 

Kirttrotiseece. XXIV | (t)1,375,9753 1,375,976. 

Ronig, Eugen. See C. Schraube 
Rongger. Nikladamcs peer ts Switz... | Sandor..4e5h XV 747,643. 
Ronus, M. See W. Herzberg. 
Roos, s Israel) ese. ae Cerise fat Wis sn one eee XXIV | (m)602,109. 
Rosé. Heinrich the ea Garg ee Hichst? oe a. XXII | (An) 263,964; 263,065. 
Rosenberg, Ignaz (see  F./Ger....... alleys ona. VI 588,180; 588,181; 588,182; 

Krecke and K. Elbel) 588,183; 613,642; 613,645. 

and Bruno Helmert ....... Gera we? KalleSren eee VI 613,643; 613,644. 

Rosenhek, Joseph ............. Ger....... Cassella...... XVII | 412,978; 412,979. 
Rosenstiehl, Daniel A. (see Z. 

Roussin and A. F. Poirrier) . re kere COTTON SEO OG VI 483,368. 
Rosenthal, Emil. See W. Ep- 

stein. 
Rossner, Heinrich. See A. 

Schmidt. 
Roussin, Francois Z. .......... Heh cote soe es Poirrier. 7: . 4: VI 210,0545 225,908. 
Roussin, Zacharie (see A. F. 

Poirrier) sosn4 eee ee Bein eee 

and Daniel A. Rosenstiehl .|Fr........ She Denise a VI 297,8523 309,882. 

Rowland, George ............. Tenn..... Rowland..... XXIII | 752,804. 
Royle, Thomas. See R. Simpson. 
Ruckers Karl asec cone Sees er poet a Chem. Found. | XXIV | (pl)1,455,5009. 
Rudolph, Christian H. ..... Peed US paw ee Oehler....... I 382,832; 305,080. 


VI_ | 396,203; 462,414; 462,415; 
465,116; 468,049; 497,032; 
516,380; 516,381; 558,612; 
558,613; 558,614; 572,723; 
579,773; 601,859. 


HIGCHStce nents VIL | 262,605; 276,888; 276,880; 
276,890. 
XTII 256,599. 
XXII | 268,543. 
and Julius Herbabny ...... Geri vies Oehler.ne es VI 504,123. 
and Bernhard Priebs ...... Geri wins ce Oebler....... VI 395,634; 396,294. 
ands Emil Viogestereae tines Getic se sas Ocehler. 00. VI 568,540. 


Rudolph, Georg’)... dc abi fe ee Getic: Bayer ites a flaee XXIII | (Az)976,219; (Su)873,613. 


PATENTEE INDEX 


PATENTEE ie ASSIGNEE 
RMRMRE GEIS. yiaavein's Sis sie: e's 0 ete cise Le tees woe 
F. Bayer, F. Westcott 
Almere Acme Sle reiee gar as.c 16 be Getic cr lee ierer ss sacs 
ame Walter: gacccscesc sess. ve ts | eae Int. Coal.... 
and Harry A. Curtis ...... 1 Oh See Bregest ys... 
UMM! PTICGFICH iss vicccess eer i. Elberfeld..... 
(see M. Kahn and M BAVet wee. srs 
Herzberg) 
Elberfeld..... 
and Martin Herzberg ..... Geri ss sa. Bayer........ 
Runne, Ernst. See A. Schmidt. 
Rupright, Howard J. See C. J. 
trosacker. 
AMEE, EMME ONG Gntis ih sb ass. NV vice Sees eee eeeees 
Salathe, Fritz and John R. 
eee es mek ssc 8 Sls blac «a Switz..... |Keller....... 
Sandmeyer, Traugott ......... Switz Bayer-Berlin 
| CIR Ne as esos 
Sapper, August. See A. Lut 
eapaare 2 fala Sera ras « « ete sins Badische..... 
Peasy ASSO pss oe se -- Switz .|Durand...... 
ge cer... Cassella...... 
Savigny,) Claude ..:.....-...-. Ld pepe Martinon... 
AW VOU OL LOULY. sire. ceca ss sess MasS......J esse eeeeeeees 
Schaar - Rosenberg, Friedrich 
See B. Beyer. : ‘Bact 
Schaarschmidt, Alfred ........ Switz..... aS tee see nie As 
Ate PAVED. od ales aes Switz..... Basle........ 
BONBG yy LAAWIS? ooele scene cs esas Ger... .peeee eee ees 
Schaffer, Henri N. F. ........ Pe a's | oe wie Sincaigin, we,0 
ee  P swite..... |Hofiman...\. 
Schamberg, Jay F., George 
nate Raiziss, and John A. a pee Dennanteey 
Scharfenberg, Oswald. See W 
Herzberg. 
Face... en 
Pari boy Soe a a B. Bibus. Tenn 
chiffers, Josep isiitiese rere| A Ss try seit Se dee eat 
Schirmacher, Karlii.........<- Ger....... Hochst....... 
(see O. Ernst and F. 
Schmidt) 
and Arnold Brunner ...... Ger....... Hochst....... 
and Bernhard Deicke ..... Ger....... Hochst....... 
and Heinrich Elvert ...... Ger....... Hochst....... 
and Hermann Landers Lee 2 Ger 70 oxe a6 Hochst ew cence 
and Richard Leopold eee Ger old stele ee Hochst eh a deate k 
and Arthur Voss ......... Gere ccs Héchst....... 
F. Schmidt, C. Pretzel) 
and W. Schumacher ..|Ger....... Eochst. ssc. 
SCHIACLOET EMOTO Wet cease rece ie) Bate oe lees eee 
SenleCel TT ATIDUF . onsen ccs ene COl cease Badisché...+. 


DYE 


_—<— 


vI 


XXIV 


GROUP 


565 


PATENT NUMBERS 


256,375; 256,376; 256,377; 
256,378; 256,380; 257,242; 
257,243; 260,242; 261,175. 

256,379. 

256,381. 


154,153. 

1,409,588. 

1,439,128. 

689,025. 

561,615; 567,615; 719,048; 
719,049; 1,028,493. 

476,413; 476,414; 501,104; 
541,572. 

677,279. 

932,812; 932,813; 950,404; 
950,405; 958,830. 

(Az) 972,130. 


1,016,295. 


227,588. 

406,669; 406,670. 

647,279; 647,280; 647,281; 
607,545. 

410,739; 538,027; 538,215; 
564,801. 

573,299. 

(Az) 793,743. 


644,331. 
413,562. 


904,809. 
(Nt) 412,680. 
210,808; 236,634. 


898,845; 966,478. 
915,385. 

354,746. 

(An) 481,591; 527,457. 
(Ab) 592,022; Re. 11,647. 


(m)602,646; 602,690. 


(m) 1,390,972. 


837,736; 936,367. 
943,470; 1,342,134. 


1,270,123. 

624,256; 627,783; 647,236; 
665,606; 672,714; 680,283; 
693,670; 724,743; 733,280; 
778,610; 837,128; 
1,045,196, 

823,294. 

1,422,880. 

881,159; 888,852. 

867,305; 881,158. 

1,076,321; 1,077,492. 

892,807. 

1,001,458. 

867,306; 881,157; 1,001,457. 

1,123,390. 


827,468. 
(pl) 1,294,836. 
(An) 893,384. 


DIGEST OF PATENTS 


COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
Schleicher, Erhart ...... Ai Ger..... +.| Badisehe..... I 516,577. 
(see C. Schraube) VI_ | 671,806. 
and Atigye Derren t autererms cee Cer Ur ire ees Badische..... VI |741,9036. 
Schlenk, Wilhelm .....:¢00s0. Gertie aks Weller. i; 6.8 XXII | 895,689. 
Schievussner, Carli) sete nes eps be peat ath Hochst recs 3. XV_ |649,218; 651,122. 
Schmatolla, Otto. See R. Reiss. 
SchmidmAlbert uw. wees exe SwitZieaa Nwanee eee cael XXIII | (Ab) 1,417,206. 
Schmid, Ernst. See C. L. "Mill. 
ler. 
Schmid, Henri ...... ei erareiate Udi rel ve ea ee Hochst. sens XXIII | (Az)598,118. 
Badische..... II__|863,761. 
XXIII | (Ab) 963,656. 
Schmid, Jakob oo... ¢ de eens ... | Switz Basle........ VI | 402,980; 449,629; 452,197; 
493,563; 493,564; 525,626; 
5575435; 5575436; 557,437; 
5575438; 557:439; 557440; 
558,438; 620,368; 620,369. 
XI | 404,309. 
XXIL | 425,525; 455,442. 
and Jacques Bachelut ..... Switz/... Basle. ccs. sss XVIII |519,971; 525,627. 
and Karl Jedlicka ........|Switz » Ppaslesscas <a : I 5375723¢ 
VI |562,200; 583,634; 583,635. 
and Johannes Mohler .....|Switz..... Basle. oc. 0% V 491,378. 
XVI |{538,183. 
and Robert Paganini ..... Switz.....|Basle........ XXII | 493,562. 
and Herman Rey ......... Switz..... Badische..... | XIX |609,997; 609,998; 624,877. 
and (Hugo: Well 262s 2s ene GhOEs asa cee Basle. ....... | XVIEIL | $83,267: 
Schmidlin, | Fulids cc... se odes EN ise ates Cassella:. i:..'s XVIII | 1,428,984. 
and Walter Brunner ...... GOR sae set sees siete giesb aust XV_ | 1,405,446. 
and Max) Fischers: +a. Gari eo ik ata eee eee XVIIT | 1,219,166. 
Schmidlin, Robert... 0:30s\s10 300 Ger. cise HGthaty. cna o8 VII |841,456; 868,294. 
IX 1,059,571; 1,162,109. 
Schmidt, Adolf ....... Se gre Ph Gee aoc eles econ wee wets XXII | 595,787. 
Schmidt, Albrecht ....0.220<0s Gér.. >. , sl Mibchet ary VI | 728,021. 
VII |807,782; 868,295; 872,085; 
872,086; 916,031. 
XV_ |778,713; 818,980; 829,740. 
XIX | 656,426. 
XXIII |(An)1,175,997; (In)906,307; 
: 1,005,481; 1,027,441; 
1,058,019; 1,058,020; 
1,058,021; 1,239,526. 
and Wilhelm Bertram ..... (POT. 5a 9 9 Hochst VII |867,670. 
and Fritz Bethmann ...... (eras Héchst....... XV |728,623; 776,264. 
and Ernst Bryk 32.00 \sk TFET. Paves ole Hochst....... VIL |877,743; 881,624; 916,020; 
916,030; 947,030; 959,617; 
963,813. 
and Georg Kranzlein ..... Getic. seas Hochstac. see III |958,325; 1,038,003; 
1,046,498; 1,052,520. 
VI 1,028,139. 
and Erich Kronholz ..... (Seo ctws Hochstsidcass VIL |812,598. 
and Gustav Kronlein ..... Get. c. pass Héchsty sis in. XV __ | 1,128,371. 
XXII | 1,128,370. 
and Ernst Runne ...... Getigcdaw Hichet..2..s24. XXII | 1,128,360. 
and Rudolf Miller ....... iS eee Hochst.3.-cc VIL |765,996. 
and Carl Pretzel ic 7 oo Gere. yet Hochst, (0.0 VII |872,585. 
and Otto Rhodius ....... Get... s Hochst. gecey XV 773.840: 
Heinrich Roéssner and Hans 
Raihorn jt cee ees Getiersen HGchat.. osc.s VIL |918,920; 1 043,468. 
and Otto mSch wane ages Ger...... Ry EL OCEIST erpareteae XXIII | (Su) 901,746. 
and Otto Steindorff ....... Getidessus Hochstewucues XXIII | (In) 1,054,039; 1,057,886; 
Su) 1,095,237; 1,141,148; 
1,057,887; 1,085,361; 
{ 1,094,683; 1,006,060. 
atid Kart Chieda yes. ee Gero ieee Hochst Jann «ee VII |955,699; 1,028,911; 
1,061,781; 1,070,541. 
and Ernst’ Bryk “45.24. COP ad wee Héehstvcccts XV_ {1,128,368. 
and Pesta: Ag rt eee ee 48 PR hE HGchst®.7cee VII |932,334. 
an rns Tye Neches ans EL, erent Hochst. i oa 68,697. 
Schmidt, Carl. See C. Schraube Mes ae 
Schmidt, betaine (see G. 
teinike and chirmacher)|Ger....... Hochsts ups. e VI |647,237; 737,967. 
and Otte “Rrast.4 s.r, one Ger... Héchst....... VI |582,958; He Heer 
and Karl Schirmacher ....|Ger....... Hachsts ve. sae VI |826,279; 826,280; 826,281; 
: ‘ 826,282. 
Schmidt, Ludwig ............. Geel ae Se accae ey eine XXIV | (P)1,326,973. 
Schmidt, Maxmilian P. ....... OFS hey ee Rallessoydiae III | 1,209,212; 1,261,858. 
and Heinrich Roese ....... Gefovas ie Kalle. 2.5... 1 VIL \apaeares 


PATENTEE INDEX 567 


COUNTRY 
OR STATE 


DYE 


PATENTEE GROUP 


ASSIGNEE PATENT NUMBERS 


eee UNG nas Pals kha es os Gera. ae Badische..... VI__|936,951; 1,075,305. 
Chem. Found.| XXIV | (t) 1,336,759. 
mcumidt, Robert En ci vessseses Se Op a see Bayere sides III | 446,892; 446,893; 476,418; 


476,419; 476,420; 476,491; 
502,765; 503,295; 506,265; 
59553493 595,350. 

Elberfeld.... | III |590,425; 500,426; 599,427; 
607,659; 605,568; 623,219; 
623,220; 656,668; 656,669; 
658,513; 658,514; 675,572; 
785,121; 785,122; 785,123; 
812,684; Re. 12,548; 
826,750. 


XXIL 742,910; 74316645 757.0873 
757,050. 

XXIII | (An) 649,486. 
and Arnold Fischer ....... GOT ey sas » pelberfeld.... . III | 790,079. 
and Andreas Jacobi ...... GE ee da .|Hlberfeld.... IIT |666,702; 675,573. 
and Adolf Sertorius ...... GOP oes s Elberfeld.... TIL |687,657; 687,658. 
SU tg 9 Ger....... Elberfeld.... IIL |812,590. 
and Paul Tust .......... era. cnn s 6 Bayer siecs se: TIL | 496,139. 

Elberfeld..... III |605,921; 656,670; 656,730; 


675,574; 675,575; 836,220. 
XXIT |755,801; 765,201; 765,637. 


Schmidt, Witt) ee Gerlach un puilcasséllacuasec XV 892,455. 
Schmitt, Rudolf ............. Bee ees von Heyden.. | XXII | 410,295. 
and Carl Kolbe .......... GetrAnccr. von Heyden..| XXII 350,468. 
Schmitz, Alexander .......... ieetre res ss Cece cceeceeces XXII 861,397. 
XXIII 964,565. 
Schmiickert, Friedrich E. .....|Get----++- Pravin te is ee (In) 386,933. 
Sebneider, Hans ............. Ger....... ges asesceees a (m) 942,674. 
pchultenpaut, Jnarl ..........; Ger....... riesheim.... 887,348; 959,078; 976,401. 


XXIII (In) 1,011,500. 
Schobel, Heinrich. See E. An- 


derwert. 
prota aes (see A. Ger 
Sete ee ee Ger... ..... 
UE he OE ee Gees oo. Berlin....... VI | 1,408,405. 
Scholl, sy ree aay dea Otic esas Hochst. ; 2:3 vI Diy Stes eas. 741,552} 
BRE AYIZ ecnele otic aerate & ie 18,981; 958,774; 
is Q. Ernst and EK. Ko- 1,028,140; 1,029,639; 
g 1,032,433. 
XII |656,857; 656,858; 656,859; 
ay 658,593- 
and Arnold Hess ......... Ger...... .|Hochst....... i ee 
and Willy fone We A es rer) ae Hochst... ne eee 
Somer wnolend HH, -..4-3.4.....: Ger....... Badische..... XIT B28,7763 
a ee Badische..... | Hl |787,859. 
ae Re ye eS ae) Ger....... Badische..... ee ee 
and Max A. Kunz .......|Ger------- Badische..... er nadie 
Schrader, Hermann .......... ne SLA AICS Wa diech ot: III As 
selraube, Conrad -:........... CEae > <ines Serew eto: V =: 1428,530; 430,075; 431,404; 


443,408; 543,784. 
E> 5245220: 
XIX 1|533,820. 
XXIII | (AI) 352,361. 


: I | 700,565. 
dH T. ERROR ie Sic 's = Badische..... bd 2905+ 
ae hcocn Ea said APA Ger has Badische..... tA TP aL Pas 
and Erhart Schleicher ....|Get-.--+-- Badische..... af seen 860,575. 
and Hans T. Bucherer .. pee Berne Aes See yes? XXIII ig Cee 0733 531,074} 
; Cf dad: adische..... 9735 1974; 
and -Carl Schmidt ........ Ew 31,075; $31,976; 531977. 
and Walter V. Tetzner ...|Ger...---- Badische..... 7135507; 718,025; 715,389. 
Schréter, Ernst W. a pia ote c ae Liew bee bie oe XXIV | (m)3 18,662. 
f Cordes....... XXIV ind SEa2 04: 
premiere meee er fiers... binles sees et in dee VI 73,795; 1,241,153. 
TE RAS Ch | ee Gers... « a he iy Wil ulote.sOs0 eisoa cent 
1,193,820. 
Schiilemann, Werner ......... Gere sts. Bayer nin sisic-sic XXIV |(m)1,474,567. 
“eer ance Gustav K. See W. 
ehaghel. 
tian: MERON Sere ee oy Geri vec. Badische..... XV_ |[687,072. 
Schtitz, Ludwig. See W. Schiile- 
mann. 


Schtitze, Leopold 
and Robert Fischer ....... Gertie ed eae aS XXIII | (Az) 1,096,198. 


568 DIGEST OF PATENTS 


— —o— SS e>SESE—SS>=Eo_ _S——_—=]"]='~a"=_a=a]™"a>a]"{—{a—_={=ajay_ey_—===—=—=E=—=—E—Eae—EeE=>=E=E=Eae=Eae=E=Eae=E=E=Eeyey_—ae=_—aeE>—eE=E>=EeEeEeE=E>=>>>l—> > >l>l>=>—>E>E—=—SS=SS=SSSSSS———— 


COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
Schuler: Tosefwce nous avers Switz..... | Basle... 0. | XXEV | (m) 1,384,637. 
Schulthess + (Oscars occas heir Ger yaa : 
and Leo Kerkovius ....... Gerics saan Bérligvas es. XXII |851,444. 
Schultz, Gustav (see F. Bender)|Ger....... Berlin. oss: sii V STT.0535 
Schumacher, Willy (see K. ; VI |418,657; 462,824. 
Schumacher nO son v0 eee owen Geta. es Hochst....... VI |846,511. 
Sohne. Fe. cts ive wale’ ary atice ce Gefen Sinise Badische..... VI |246,221. 
Schwab, Otto. See A. Schmidt 
and R. Miller. 
mtr Des Franz. See W. Herz- 
erg. , 
Schwabe, Rudolf ............. Ger cracae< Moenst. <.. 7: XXIV |(m)1,076,160; 1,181,485. 
Schwan, Nicolaus (see B. Ho- 
MOT AN WS Chath ie Meme are ae oe EPs viet , 
and Wilhelm Zedel ....... Geray.css Hochst....... XV_ |658,286. 
Schwarz, Ernst. See A. Lwut- 
tringhaus. 
Schwarz,’ Maxinivei.. vee seeas Aus.-Hng..|---+eeeeeeeeee XXIII | 1,019,092. 
Schwarz, Paul. See C. F. M. 
Schaerges. 
Schwarzwald, Gustav. ......... N. Yin... [eee ere ee eens XXI_ | 240,467. 
Schweitzer, Hugo ..........-- oS panes Bayer........ VI |1,429,781; 1,429,782. 
(see A. Zart and K. Desa- : 
mari) Dickerson (1%4)| XXIII (Ab) 539,550. 
and ‘Artbict, (Zant laine es wis TOT sh e'8 Bayer.......- VI_ |1,009,796; 1,009,797; 
1,024,031; 1,038,209; 
Re. 13,550; 1,038,210; 
Segaller, David, and D. H. P kecsante 
egaller, David, an . H. Pea- im 
ivi LEP PIIAE fo seine ae Mon ee Bidens British Dyes. | XXII |1,465,680. 
Seiberth, Max. See M. Hart- 
mann. 
Seidel Dr) Charles ii.2 . ss eee IN OY civatendt ot ecerecescs XXI | 76,107. 
Seidely Heinrich)... ccs ve seed Aus.-Hng..|Kalle.......- XV_ |687,581. 
Seidel; WPattl Rei e o sin tee ee Geren ssn Badische..... VII | 698,328; 699,581; 798,077. 
(see R. Knietsch and D. 
Vorlander) XXII | 690,325. 
XXIII | (In)692,720; 744,417. 
and Ludwig Preuss ....... CT ry Kall a XXII |661,821. 
and Robert Wimmer ...... Ger... .. ef e cere eee ceees XXIII | (In) 794,049. 
Sethertarb rluno sine eereeciceleces Geri. sa von Heyden..| VI 493,413. 
XXII | 407,906; 488,290; 578,839. 
mM Ais oat As XXIV (m) 501,235; 604,503; 
urt ili an ax : 749,634. 
Giasiner tc Srey Ger howe von Heyden..| VII |714,042. 
and Otto: Meved.icece ces Or Gisae se von Heyden..| XXII |887,050. 
Scilet Pant Hi oe eee ern ws Badische..... XXIII | (In)794,050. 
Sellon, John S. and Robert 
Pinkneyiciceea cote eer tee Bagi se Paar ers ass XXI_ | 167,360. 
Selwig, Johannes ............. Ger caress Selwig, Lange | XXIII | 541/573. 
Senderens,.J canbe ae ae ee ae Fr. iss. Poulenc...... XXII | 1,265,956. 
Senger: Robert. 4 ocice ee eioen N. Yewese [outa nenneccws XXIII (AI) 475,616. 
Sertorius, Adolf. See R. E. 
5 See a 
CY DErth, Lvermanny ss mies crs CT... e006 - 
and Moritz von Gallois ...|Ger.....-- Hochst....... XXII | (Az) 595,894. 
Shaw, George S. See M. J. 
Marshall. 
Shorey, Edmund C. .......... D.C... ae [ohne eee XXII | 1,450,990. 
Sibley Robert L. See C. W. 
Bedford. 
Siebert, Hans. See A. Wein- 
berg. 
Siebert, Otto. See A. Clausius, 
. Gley, W. Herzberg and 
B. Schoner. 
Sicgle, Gustey Ausra N. Y..... |-°- sitet eens XXI_ | 66,897. 
Siesniund: A UeIgt Science ae Ger...... Radische..... XXIII | 650,556. 
iegwart, Josef. See E. Reber. ; 
Siepermann, Otto ............ ING Teetce) ts Consolidated. VI 1,073,784. 
Sigwart, August. See W. Neel- 
meier. 
Silberberg, Rudolf ........... NP ince Hoops (%4).. | XXIII |320,820; 320,82. 


Silbermann, Theophile. 
See A. Ostrogovich. 
Silberrad, Oswald ............ BAgeo. asne| ces Sota ee XV_ |1,268,803. 
Siller, August. See C. Rumpff. 
Simon, Charles (see C. Ris) ..!Switz..... Geigy sci sees VI 1628,233. 


ee 


PATENTEE INDEX 


COUNTRY DYE 

PATENTEE pe eras ASSIGNEE | croup 

Suuon, Sigismund E. ......... Dob Ad Bint casey | Ctra sey are III 
Simpson, Richard, Arthur 

Brookes and eonomas Rovles. | HN. .s.0 (ecce cece e vans XXIII 
Sener RLIGCTICN, (5 ccc kek os Serie ct ss Griesheim.... III 
i igs Ub aa ae Bk a Gerdes ies Griesheim... III 

eel) 
ana Altred Holl oa........ Geri eos nsk Griesheim.... III 
and Ernst Milarch ....... (Gerencncdee Griesheim.... | XXII 
Skirrow, Frederick W. ........ Cait mes Shawinigan... | XXII 
afd lames oDick™ .c.5 sess Cant scsi Shawinigan.. | XXII 
Skraup, Zoento H)............ Aus.-Hng..|Badische..... XXII 
XXIV 
IUD OR ISS Bole cca ne cs os INGEN. 3. us National..... XXII 
Snelling, Walter O. .......... IS gots res sere alll Meets « sie es XXIV 
GCE IG Mees cc ine on seek eas aery..«vs oe Frochst 234 3s. I 
V 
VI 
XXII 
Somerville, William .......... PUGET « inci) laa de oly wales « XXI 
Sommer, Rudolf ..i..c0s...-. Aus.-Hng..|Fritzsche..... XXIV 
Soutar, Charles Wm. See F. 
W. Atack. 
Specht, Leopold. See F. Erban.|. 
Speitel, Rene. See C. Vaucher. 
Sehce  PAViOn <.s.<s.csadss.. i Bae ores fc ge Romie XX 
Spencer, Archelaus E. ........ MU ties oa | Sento ae ed XX 
Spengler, Oscar. See W. Herz- 
Spent <: Ppt 
perr, Jr., Frederic : 
and Ralph L. Brown ...... Eoin aictew Koppers...... XXIT 
ae and Marc Darrin ......... Pa........ pepets ce eeee ae 

i OO Ge) Ger....... Ochst....... XXIII 

XXIV 
Spieler, Heinrich J. and Josef. 

: See Guillaume de Montmol- 

in. 
pes Harry S. See M. R. Mof- 

at. 

Stachlin, Otto (see K. Zechent- 

Mawes set | ehh ee Hochst... : vI 
Stalmann, Gerhard ........... Cer. ages Schimmel.... | XXIV 
Stange, Otto. See K. Hage- 

mann. 

Starobinetz, Charles .......... y nS eee Barking... 2.7. XV 
De RPMAMOINORL oc, cc cs cc dccus 5G Paes W. Va. Pulp. | XXII 
Staudinger, Hermann ......... Switz 
and Hans Veraguth ...... Switz Basten” toe eee 
mtearas, Theron C. .2......... ‘Gad ARS Kellogg... wt: XX 
Stebbins, James H. ........... bs Edy Se OLE en RRM VI 
A 
XVIII 
XXII 
teins, FOOT Au ass ba scenes 0G ie aera U. S. Ind. Alc.| XXII 
Steimmig, Gerhard. See S. A. 

Holt. 

Steinbach, Ewald, Franz Acker- ‘ 

mann and Max Utzinger ...|Switz Basie sien ease III 
Steindorf, Adolf .....3....... Gere. s 

(see A. Schmidt and K. 
Thiess) 
and Robert Welde ........ Cetera tis Hochst.....>- XXIII 
GIG Ot, GAREOIG  Socrd dss cee ss Switz Sandotay «45 XI 
XVIII 
XIX 
XXII 


569 


PATENT NUMBERS 


686,356. 


(An) 182,234. 

999,680. 

1,044,933; 1,070,196; 
I,150,152. 

999,062; 1,119,546. 

1,329,435. 

1,103,383. 

1,429,650. 

1,449,918. 

237,917; 237,918; 241,738. 
m) 295,825. 

1,419,695. 

(pl) 1,430,034. 

712,421; 739,117; 766,540; 
794,052. 

1,015,354. 

646,711; 739,118. 

805,890. 

1,193,838. 

(£)804,682. 


326,601. 
251,384. 


1,414,441. 

(pl) 1,263,813. 

302,790; 303,335; 306,969. 
(Az)302,791; 306,546. 
(m) 495,124. 


1,155,765. 
(m) 886,085. 


1,318,022. 
1,411,529. 


1,461,435. 

611,870. 

221,114) 22,050 cate nro. 
22150175 221,11 oseeet, f10); 
221,120; 242,707; 256,401; 
302,170; 313,118; 
1,235,253. 

252,273; 252,274; 253,443; 
253.444; 253,445; 254,064; 
254,065; 255,349; 255,350; 

266,912. 

256,400. 

1,421,604; 1,421,605; 

1,432 308. 


1,437,783. 


(An) 1,145,934. 

647,338; 901,657; 992,613. 
603,016. 

1,054,247. 

731,139. 


579 


DIGEST OF PATENTS 


COUNTRY DYE 
Steinike, George 
and Frederick Schmidt™..,..[Getisccics feseweececsbaa VI | 576,511. 
Hochstteeucc VI_ | 603,093. 
Steinkopf, Wilhelm ........... ee rE ag Choe eR XXII | 1,085,708. 
Steinmetz, Charles P. ......... Nii VOR) ao ees wares XXIII | 894,547. 
Stephan, Alfred :...4...-06-06: Gere os ior pathlstet ae Per XXIV | (m)812,608. 
Stephan, Carl (see A. Rahtjen)|Ger....... |-...-seeeeee VII |1,427,863. 
Stephens, Henry...) sess #0 POR iis hs ois a wise is = er XX |4aar; Re. 3. 
Stevens, Maria As” lies ce ace cies Mint. <4: obsecaeweae che XX |562,045. 
Stewart, Ebenezer. See E. S. 
Wilson. 
Stiegelmann, Armand J. (see K. : 
Reinkidg)< eo cota n pa aate Te, Badische..... XXIII | (In) 657,320; 680,894; 
699,033; 720,501. 
Stine, Charles M. ........--%: Denese du Pont....: XXIV | (e) 1,370,067; 1,450,675. 
and John L. Gilson ....... DE teis'sen du, Ponti es. IX |1,393,714. 
Stober, Wilhelm. See C. Miller. 
Stock, August. (see B. Homol- t 
Mea div hidicta tans ontbue pane wuss iene Ger Srey, Hochst 2rsc5, VII_ |[662,703; 1,050,179. 
e XXIII | (Tr) 1,043,271. 
and Friedrich Heim ...... LO ott ep ay Héchstsy ss oee XVIII |995,494; 1,042,498; 
‘ 1,065,405; Re. 13,969. 
and Otto Nicodemus ...... Gero. 25 Hochst sls 60s sie XVIII | 1,217,238. 
Stolz, Friedrich ........seees: REE Sia sy we Hochst....... XXIV | (m)579,4227 1,017,699; 
5 1,053,240. 
and Georg Korndérfer ....|Ger....... Hochst....... XXIV | (m)o990,310. 
and Karl Streitwolf ....... Asef ees Hochst....... XXIV | (m)936,380. 
Storey. Brite veeerch dca caees « Aus.-Hng.. | Hochst....... VI_ |569,302. 
Strasburger, Josef ...........- Russia.. Berlin....... VI__} 399,581. 
Straub. Prite) .eewics woe vily ok Switz Basle,....4. XXIII | (Az) 1,440,566. 
(see G. Engi and J. Grim- 
mer 
Strauss, Prank “A. iicacsiee ne at rere OnE ere it: XXII | 1,367,898. 
Streitwolf, Karl. See F. Stolz.}_. 
Strosacker, Charles J.) ss... «804 Mich.3 0... Dow......... VIT_ | 1,442,743. 
Mich D VIL apes s 8 
and Howard J. Rupright . [ls nt OW. sseeeees 1,431,606; 1,473,887. 
Strupler, Albert : ie.e Uk che Ag ates os see eee Hochst.....5. XXIII | (Tr) 1,085,178. 
fuer. Pera art Colles. seats o outs CT... eee 
: and Walter Grob ......... Ger) ss a8 Chem. Found.| XXII | 1,421,743. 
Stiircke, Adrianna ............ Nw Mae anh Eee eyes elena XX | 1,219,186. 
Sttisser iCHardine .souia sustelere ane Geto Sa 95,6 Bayer........ VI 1,457,235. 
Suida, Wilhelm. See M. Becke. 
Sulzberger, Nathan ........... Ger...... o [cece rece eeeee VI |879,424. 
N. Yoeees [eceeeesscceas VI |902,021. 
Summers, Bertrand S. ........ Mich... of ecct esac ek aa XV_ | 1,053,676. 
Sunder, Charles. See M. Bader. 
Susemihl, Theresa M. See T. 
iy veereods S Ach k 
utter, eodor. See I. Ach. 
Suzuki, Umetaro ... he a eet se Japan elie bi[ ee aa el se: wreelacy re XXIV (m) 1,330,288. 
Suzuid;) Zenshita <).20e ewes eas Calif... 2. [oeeee eee eeeee XV_|1,244,795; 1,244,796. 
Sztatikayy Abs ).cielonwtssane: Hung..... Chem. Found. | XXIII | (Tr) 1,357,482. 
Taggesell, Richard ............ Ne Yiastetes Schoellkopf.. VI _ |618,963; 683,190; 1,327,688. 
8s XXII |659,496; 659,497. - 
Tagiani, Ernesto. See R. Lepe- 
tit. 
Talbot, George W. .........0-- R Loe vabeccae ene eee XXI_ |99,496. 
Tambach, Rudolf AN ay Sed oy NR Ger acti isce'e Chem. Found. XXIV (m) 1,391,705. 
Tanburg, Arthur P. .......... Dele du’ Pont; 255 XXI_ | 1,422,494. 
Tannehill, Arthur LL. (see H. 

N. \Copthorne)) 2... eek Ahem se TST CL, ‘Srate tetera lub sven stave suet eae tees XXIV | (pl) 1,389,791. 
Tauber Irngts i evivwunwas oes Ger 2530 Eochstemn sya XXIV |(m)596,797. 
‘Teichner, Gustav: es aceecieiewiaen a PAIGE ielevelcravsn ie eis iets ae ote sialete XXII | 1,436,214. 

Terrisse, Henri and Georges 2 

Darter raven cas Ge oes Witt... Badische..... I | 637,183. 
Tetzner, Walter V. See C 

Schraube. 

Thatcher, ‘Charles? J. 40..le< 0s. NVica boas tae ean XXII | 1,405,954. 
Thauss, Alfred. (see O. Dressel 
and Mi Bulk} ooh oes ee Pe Elberfeld.... | VI |794,568. 
Bayess vase XV_ } 1,081,638. 
and Alfred Giinther ...... Geri see Rayétian.e sas XXIII | 1,450,463. 
Theta si riedricho laos) r nese nat Geico ven Lee cinelere aiete XXIII } 983,951. 
Thisle, AIbrechtoas sb ehewee Oi Ne cay Chem. Fab XXIV |(m)1,045,759; 1,091,870. 

_ and Georg Wichmann ..... Gers vere: Chem. Fab XXII | 1,075,171. 

Thiele, Johannes Sh aoa Ned tase crate Germans Badische..... XXII | 546,604. 
Dhies,: Peismrich ie cute eae Geren soe Cleff (%4)....| XXIII} (Ab) 452,324. 


PATENTEE INDEX 571 


eR a 


PATEN TEE alain A DYE 


OR STATE ASSIGNEE GROUP 


PATENT NUMBERS 


Thiess, Karl. (see A. Schmidt/Ger....... 
Maennchen, A. Steindorf 


1,151,628, 
(In) 1,426,522. 


Xx 
XXIII 


ead °F.) Gilroy: . 2.5. ... a Ger wee. ce Evochstseriee. III 853,041; 8 : : 
Thomaschewski, Paul ......... Gersee. sare Bayerosecace: fer AE ae pea 
(see CG. Thun) and C. 993,736; 1,004,107; 
Unger) I,010,463; 1,028,637; 
a Ry at 1,044,603; 
1,0 92 ; I, ’ . 
Elberfeld III toys rs - EE 
AV OUats ws ale we 961,387; 961,388. 
in : 
SG ee eS ICE Synthetic xt Cans siege 2r7- 
H. Raeder, W. Mieg F 
AE. = BISCUET fries 5 4 sins SrOE a 5 ates Dayerva > as Ill 970,278; 971,224; 971,225; 
€. 13,257; 986,521. 
Mtns, SOCAN .6..0.2..5:. CEL rd Os Leah cise eens o's m) 503,066. 
Thon, Eduard. See W. Herz- XXIV | (m)503,066 
berg. 
Thorp, Henry. See J. T. Reid. 
Thin, wnat (see RR.  E. 
Ps UE aa Gen a ses Elberfeld. . III | 608,238; 623,638; 746,405; 
844,835. ; 
hee Tust and Paul Thoma- - eae poet 
Se Oe CBirateie ais yathetic. «2. | XNTT An) 1,090,352; 
Tigges, Hermann. See P. Jacob- T} (An)1,090,3523 1,090,353. 
son. 
ies hice ( Cc Me Fiz : 5 Ee bac Roe RS chre BE XXII | 722,336. 
katsch, im (see?P. Julius) .|Ger....... adische..... VI 671,902; 671,903; 
Tobias, G. See F. Kruger. ol 771903; 671,904. 
GCUET ELAS cakes ss esss0- os Ree Bayer. is to's XXIII | (Su)873,636. 
Ne Y.o.00 | Bayer... 0s XXIII | 900,130. 
Grasselli..... XXII | (Az) 1,417,860. 
Poel goyaney “Aly .4.......+- hs eee (aes XXIII | 1,289,968; 1,367,930. 
Townsend, Clinton P. ......... De Cr Hooker =< 5... XXII | 1,468,220. 
Toye, William. HOR. ae. cise. ee ae Fabric Orn... | XXTIT | 250,302. 
Mig Led Oo ED ie, en Lh ee ee oe Chim... | XXIT | 666,570. 
TICS. wees ae XXT Oo : oO. 
Tropp, Willy (see F. Scholl) ..|Ger....... Héchst...... ee ee 
Tramball, Harlan 1,. ......... Thien a> 
and William L. Evans ORO ea. U. S. Govt XVIII | 1:4025195.- 
Turner, Joseph. .... ces esese Metco: Fee teas ees ee VI | 655:529. 
IX | 743.778. 
XXTIT | (11) 888,942. 
and Harry Dean ......... ENG he ates etree wisiae sone | LUEL. | 987:4375- 1,014,062" 
1,014,983; 1,014,984; 
1,028,306; 1,099,676. 
Tust, Paul (see R. E. Schmidt,/Ger....... Synthetic.... | xxyry | (An) 1,126,591. 
P. Thomaschewski and C. 
Thun) 
Tuttle, Herbert C. See P. T. 
Austen. 
WAP PAUSED AG ci Golesi es s's DRO G vil averc dee ae ajc. XXIT | 628,503. 
Mytee hy Obial Sci 6 iicsev esses Dee, Pree te es eee XXT_ | 458,244. 
Uertberg, Wilhelm ........... BOE are <0i8 
Budeeieimricn Heimann ....)GEr..... 00 |. cccecesecses V 617,703. 
Whlenhuth, Rudolf .:......... Ger asec. Hiochst....... III 943,717. 
(see E. Hepp) XXII | 15194,943. 
Unigann, Paul ...........2.: Getiys - sis von Heyden III | 653,492. 
LON Ue Tebsiy- Lek g(s 2 SOA a ee Getinc ccs Berlina ones I 643,569. 
Til 961,047; 961,048; 1,001,325. 
XXII | 993,915. 
RIS ATIBUL censuses’. Ger..... wa |oeseoseeecces XXII | 1,466,683; 1,467,258. 
Mire agard. . igs. i seen'ss ss Geren. sss Hochst....... XI | 364,320; 366,356; 366,357; 
649,227; 649,228. 
XVI | 362,592; 366,639; 366,640; 
384,480. 
and Moritz von Gallois .../Ger....... Hoechst. 22.4% VI 569,395. 
Ulrich, Moritz (see R. Kothe) .|/Ger....... Baveraace «sa VI 415,258; 417,294; 417,205; 
417,296; 423,970; 466,202; 
466,841; 468,142; 476,335; 
Re. 11,308; 476,336. 
Elberfeld VI | 611,663; 661,664; 619,518. 
BRVES ce oe pee XV_ | 560,334. 
XXII ! 415,259; 444,679. 


37 


572 DIGEST OF PATENTS 


NTRY DYE 
PATENTEE pease: ASSIGNEE GROUP 
\ 
and Johannes Bammann ..|Ger....... | Bayer. .s> os. VI 
XXII 
and Karl Heidenreich (GN, NL Elberfeld.... VI 
and Richard. Lauchen.. ieee Cerne: Daly Eiaksteas ts cc's VI 
Johann Bammann 
and Martin Herzberg .|/Ger....... Bay eficcvaraaes VI 
Ulricha- es Mrast easter eee ae Ger As Dalila ai VI 
Badische..... VI 
Dabl ayes are XXIII 
Unyer, (Oskari ey rc taicm aes (rer, Saisie Elberfeld.... III 
and Paul Thomaschewski ..|Ger....... Bayer.y.sera8 III 
Unruh, Max C. von. See von 
Unruh. 
Urban, Johannes. See M. 
Fremery. 
Urban, Wilhelm. See J. Alt. 
schul and O. Mankiewicz. 
Utzinger, Max. See E. Stein- 
bach. 
Valentiner, Friedrich W. S. ...|Ger..... ce [eter cere eeens XXIV 
Vanselow, Albert P. and Walde- 
mar. See C. O. Benedetti. 

Van Skelline, Isabelle J. ...... DNctek Sc oh oi A spevicrae Wiel e ares veee XXIII 

Van Winkle, JohntAsie. sees ses Mo... . 22. [ere e ee eeeces XXIII 

Varma, Phuldeo S. See R. L. 

Datta. 
Vaucher;* Charles |. kc Sab eee Switz Durander. sen XI 
(see C. de la Harpe) 
and Rene Speitel ......... Switz Durand... ..: I 
Vaughan, Henry W.isoecs. 442 ROL Lee} ats ee eee XXIII 
Weres, (Rataer Cre weic eric, Was MATTE eee 
and Marcelino H. Vegas. ;.|Argen.....]:-«2e+¢s08s% XXI 
Venter Otto soo. wie eae ee Greats Soro Gwrrermerarneea XXII 
NEE svn Biete ata sasha teae: he ee Eten ers Soc. Ang.-Fr.. | XXIV 
erner, amille and Gabriel 
Rach 25 Poe oe ee shee ee ees witz Grasselli..... XXII 
Versmann, Frederick. See H. 
. Fenner. 
Vettercke, Frederick G. ....... NEWS eee eens XX 
Vicongne, Auguste. See EF. de 
Grousseau. 

Widal Menrl RG h conse eee Fey Saanich edule ee cane XV 
XVIII 
pe? 
XX 

and Alcide F. Poirrier ...|Fr........ Soc. Chim XV 
Vieth, ‘(Hermann “2.82 oee eee Germs. Knoll aes XXIV 
Vignon; “Leo snout eee Ered Site |'cdals whats he ee VI 

IX 
XVIII 
Ville t Jaties? ee oo aca eae oe [ah hops ERASE lec A ok nk A XVIII 
Villiger, Viktor (see P. E. Ober- 
reit and. Po) Julies) ies asus Geren teva. 

and Heinrich von Kran- 

néechfeldt sos ec pe wean es (FOTIE aise lo hace enero III 

and Ernst Fussenegger ...|/Ger....... Badische..... VI 

Virck, Paul. See H. Heimann. 

Vises Gerhard Nit ences ete (Geta henne Dahl wee se XXIV 

Viiet, Elmer B. See A. S. Bur- 

dick. 
IViOEELET EEGTEIS Ei Neustete slerteree rete GreE ES Scshans | Stoke one a trerohe XXIII 


PATENT NUMBERS 


482,106; 496,392; 498,759; 
498,873; 498,874; 499,198; 
506,284; 509,635; 512,493; 
524,005; 533,508; 544,699; 
544,700; 556,298; 578,432; 
593,790; 608,999. 

540,412. 

678,323; 687,171. 

476,337; 501,118. 


515,381. 

911,186; 1,014,539; 
1,022,612; 1,028,239. 

1,077,655. 

(Az) 890,254; 910,130; 
936,260; 937,741. 

654,294; 654,295. 

994,803; 995,306. 


(m) 811,884. 


192,201. 
334,140. 


929,350. 


1,418,852. 
272,499. 


1,330,992. 
764,966. 


(£) 646,772. 
1,437,571. 


9,890. 


523,138; Re. 11,659; 
594,105; 594,106; 594,107; 
601,363; 601,364; 601,365; 
608,354; 608,355; 618,152; 
622,299; 629,221; 630,952; 
1,265,836; 1,265,837. 

603,300; 609,598; 609,599; 
621,393; 664,450. 

595,897; 618,809. 

(Su) 549,036; 549,082. 

532,503. 

(m)678,070; 998,726. 

310,155. 

324,615. 

319,646. 

589,766; 591,309; 701,427. 


1,396,483. 
990,173. 


(m) 512,590. tae 


(Su) 708,429; 724,631; 
1,200,055. 


PATENTEE INDEX 


573 


COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
Voger, Emil. See C. Rudolph. 
Voigtlander-Tetzner, Walter. 
See W. V. Tetzner. 
Volger, Franz. See P. Ott. 
Winjimctiboy (eetih Ae aay erie ies Clee hee Bayetinn ted cccts vI 902,186; 1,020,670. 
DAVEE Sess e ses XII | 935,829; 935,830; 969,428; 
972,951. 
Synthetic..... XII 1,098,600. 
Vollberg, Hermann. See A 
Klages. 
Vollbrecht, Heinrich .......... N. ¥..... Schoellkopf...| IX | 333,036. 
and Carl Mensching ...... Se Baa etapa Schoellkopf...}| VI 333,035; 333,037; 333,038; 
333,039; 333,041; 333,042; 
Si lssrocee. 
333;034; 333,035; 333,040. 
Volwiler, Ernst H. See R. se he 
Adams and O. Kamm. 
Vongerichten, Eduard ........ Ger....... Hochsts; ts ss. XRT Wa 72685. 
von Bolzano, Friedrich ....... Ger....... Hichst..... /. VIL | 712,246. 
(see B. Homolka) 
von Bramer, Harold ......... NON cs te, Eastman..... XXIV | (p)1,421,869. 
von der Linde, Carl ......... Dae, ae ek pane XXII | 596,043. 
von Diesbach, Heinrich. See A. 
Luttringhaus and M. Isler. 
von Gallois, Moritz .......... CP esis so o's Hochst....... VII | 706,921. 
(see E. Ullrich, A. Philips, 
H. Seyberth) XXIII | (Az)575,228; (In)808,443. 
von Krannichfeldt, Heinrich. 
See V. Villiger. 
von Mering, Joseph F. ........ Se Sad eee Us ee aawe XXIV | Gm) 537,841; 541,489. 
(see E. Fischer) 
von Miuiller, Wilhelm. See O. 
Doebner. 
won mereer, Hugo ...<6e.00e- Aus.-Hng../Basle........ XXII | 348,483. 
von Portheim, Emil .......... PTO] 2 CY A rae epee VI_ | 498,303; 586,865. 
Czech... .. Kinzlberger... XXII | 1,404,055; 1,404,056. 
von Sztankay, Aba .......... Hung -{Chem. Found.| XIX | 1,357,482. 
won Werun, Max ............ Ger....... Hansmann... | XXII | 891,753. 
Voress, Clyde I. and Vernon 
Oe ge N. Y..... Gas. Rec XXII | 1,453,215. 
Vorlander, Daniel (see H. S. 
Holt and H. A Mle eal |Ger....... 
and Bruno Drescher ...... _|Ger....... Badische..... VII | 690,332. 
and Paul Seidel .......... Ger....... Badische..... VII | 778,725. 
Vorster, Walter. See J. Bani. 
mann. 
Voss, Arthur. See K. Schirma. 
cher. 
Voss, Robert. See A. Schmidt. 
Wacker, Leonhard ............ Geren fs'23 Badische..... VII | 549564. 
Wagner, Hermann and Jacob 
Lon oT ee gee Ger....... RlGchst%. . sac VI 1,082,719. 
and Josef Erber .....,.... Ger....... Hechst et. VI_ | 1:016,307; 1,041,919; 
1,160,471. 
and Erwin Hoffa ......... Gera ts Hochst. tvs, <5 VI | 1,149,231. 
Wahl, Andre and Robert Lantz|Fr........ St. Denis XXII | 1:460,774. 
Walder, LOS eS ae Switz Sandoz...... XI | 1:299,070. 
Waldinger, Gustav A. ......... oe ee 
and Carl F. Iserloth ...... Cy) eee Bayer: 200. (Su)873,277; 882 : 
Waldstein, Martin E. ......... i> Eee wey sia aneanee 
and Armand Miiller ...... Wem rates « caus Seo oe XXIII | (Ab) 330,275. 
Walker, Harold W. See V. 
Coblentz. 
WHOL, BeGWatd [ovecs se wsewavees nee Kalinusiccs. +s XXIII} (Ox) 1,303,426. 
XXIV | (P) 1,337,673. 
Wallach Otto s5.cs esses ie ses (FOE vas = st ties ote eine VI vege ne 
Wetec, Roget Ne csc ccesscs oss haeux be reat oe XXII | 1,291,300. 
erage rob Ree hoes Ronee XXII | 1,470,039. 
BiterePOMANMES sles cs cece cs Witei cites CIC et ees vi 398,990; 1,297; 440,288. 
MO ETEUDS FIOPDET cc iccc ec aeess New vers YOUNBo or ses XXI mAh ye ables 
Warren, William H. ay R. W. 
Cornelison. 
MEN RIG diese iv s< 04s 09 6 Opa Ps el Peni tenor oe XXII | 848,791. 
Weber, Oscar. See W. Herz- 
berg. 


38 


574 DIGEST OF PATENTS 


COUNTRY DYE 
PATENTEE OR STATE ASSIGNEE GROUP PATENT NUMBERS 
Weber, Theodore .......0-00° Lilcdwe ness ee Geno see VII | 86,047. 
Wechsler, Marcus ..........-: Engs aoe oe Gillman...... XXI_ | 1,031,602. 
Weeber, Rudolf .......-...++- AUS SH nto e oo eeeaie XXIII | 1,186,052. 
Weil, Hugo . (see J. Schmid) .|Switz.....|Basle........ XVIII | 623,346. 
Weil, Leopold (see B. Mayer) .|Ger.......|.....ssceeeee XXII | 1,419,186. 
Weiler: lax, wcuisclssmtcsis sieve Gere ads Bayere..eaies XVIII | 891,888; 891,889; 947,876; 
950,359; 976,417; 978,799; 
978,800; 978,801; 978,802; 
998,139; 1,004,609; 
1,004,610; 1,093/0778 
1,034,173; 1,044,836. 
Nav. see Synthetic..... XVIII | 1,101,770; 1,218,232; 
1,244,149. 
Weinberg, Arthur (see M. Hoff- 
MANN) se eeeeeeveceececeees Geta ones Cassellas. 6.254 I 709,187. 
V_ | 395,300. 
VI : 
380,067; 412,440; 421,640; 
426,345; 515,100; 517,533; 
525,245; 526,763; 532,125; 
535,036; 535,037; 560,448; 
560,449; 588,203; 703,105; 
718,181. 
XV, | 896:5595 660,067; 701,435. 
434,493; 469,329. 
XVIII | 464,538; 472,001. 
XXII 537,511; 651,061. 
and Richard Herz .2.....). Gere te Cassella...... XV 693,632; 693,633; 
and Felix Klingemann ....|Ger....... Cassellasin. ce VI 709,186. 
and Otto Lange <5... ..<>- Geri tuaess Cassellav-ne.- XV 712,747; 714,542. 
and Hans Siebert ......... Ger....... Casselia.. oor vI 375,848. 
XXII 362,560. 
Weisberg, Louis and Ralph S. ‘ 
IPOGteR Mieceters arcs civiciociete evade te eus IN setae Barrett. Gs XXIV (pl) 1,424,137. 
Weisbrenner, H. See D. Vor- 
lander. 
Weiss: Andre d5> .cosvack ve 2e8 oe Pegs oc Soc. Chim.... | XXIV | (£)1,345,649. 
Weiss, Franz, Cy). vam. eee Aus.-Hng..|Klimosch..... XXI | 443,026. 
Weiss, George H. and C. Dins- | 
MOHE See ie bom Vee aes Mass.....- Carter 0 oe XX_ | 384,804. 
Weiss Solin civics. ic teste ona stevetors NIGYc. Soct -Dparretts esse XXII | 1,301,796. ! 
and (harlea R. Downs. J. 1N.. Jisses« Barrett. 5.22% XXII | 1,318,631; 1,321,959; 
1,322,983; 1,355,008; 
George C. Bailey, 1,374,695; 1,380,277. ) 
and Raiph oF. “Potter (soci Ni Ji... 0: Barrett... ¢s. XXII | 1,355,100. 
Weiss; Morris’. 92-027 ee Nueieowne Dovan-..ce XXIV | (pl) 1,422,506. 
Weissbrenner Heinrich. See D. 
Vorlander. 
Weith, Archie J. See IL. V. 
Redman. 
Weizmann, Charles, and David 
os yell far fds A Aone ei Pe BER waark cbpaliathrahetic’ XXII | 1,395,620. 
Welde, Robert. See B. Homol- 
ka, G. Merling, and A. Stein- 
dorff. 
Weller, Arthur W. and W. T. 
Ro) Bindleyi.. en ee Eng... 25 [eee ee eeeeeeee XXIV | (pl) 1,368,867. 
Wells, Alfred A. See C. Ellis. 
Wore buster. Fi SD beeen ei he a Poocein be Spares 5 aa ih meh (m) 563,993. 
eliz, | HHeitirich “(your eet ds Sen adische...5'. -754,264; 763,233; 825. 
Weskote Friedrich) See nicl ONO Ne ee 
Rumpff. 
Wessbacher, G. See L. H. De- 
hoff. 
Wie 7 une A eres oi a Coos bis! eainie ae goatee mane x 1,327,260. 
ite) “John> Mchoews. pte SS ¢ m)1,297,952; 1,313,657. 
Whitehead, William T. 7) 90>. Canada... |Dupee (1%4).. | XXIII 100,687. (Ab).499,6885 
Whitty, George S.. /..5...--4-- NOV ae Devaeval sn) XXII | og3 764.0 0, 
Wichmann, George, and Max 
Gabler ou sans cone een eee Geri re ss st Chem. Fab... | XXIV (m) 690,804. 
(see A. Thiele) 
Wienall Harry. See J. Baddi- 
ey. 
Wildman ErnestvAce. eet Tndseecnee Parke, Davis. | XXIV | (m)1,317,250; 1,317,251. 
ee Otto. See B. R. Sei- (oar tias aA 
Crt 
Wilke, Rar)... sence annie es Gersente Hochst a. ane XXII | 1,417,875. 
Williams, wArthune Gennes Niecy nee Barretton doa. XXII | 1,423,980. 


PATENTEE INDEX 575 


————————————————_—_—_—_———=—==_—__============_——=_=_=_—=_=_=_=_=_=[_=[=[=[as_[a[{z™a”z=a_a_aa_a_a_a_—_——l__l__l_____—______—_—_>= 


COUNTR 
PATENTEE se a ASSIGNEE eke PATENT NUMBERS 
hs Woes a ea Re iercsisuere sets, weiss LIP attenerst 
Pigeons emeLaller. a... @OhiOneces ELUti terete ores tele XXII | 1,450,569. 
Williams, Rupert Ramer balsas 501 NY erageh ome ekelats eco ay VI |384,342; 304,425; 404,331. 
Alban yiners see VI |410,057; Re, 11,016; 
410,058; 412,148; 412,149; 
416,1453 te 11,178; 
17,207; Re. 11,179. 
Witetter Richard .......... Gere ice ity bd 
and Petes Ditisherg <4.) Gere... «+s Bayer.......- XXIV | (m)1,427,506. 
Wilson, Edgar S. and E. Stew- 
DED ct sie el ctvigiece caieieis.c ss & © ENG ccle sce] we lowire swe 6 6 <0 XXII |640,061. 
(See L. P. Marchlewski) 
Wimmer, Robert (see P. Seidel)|Ger....... Badische..... XXIII | (1n)820,900; 833,654; 
843,566; 910,889. 
Windisch, Kurt. See M. Bock- 
miuhl. 
WVitiicely SRLEPDETE es ccc c scene Dele. ees du Pont...... XXII | 1,307,570. 
Winslow, Homer ............- Rai Cassella...... XXIII | 941,399. 
Winter, Carl (see P. Julius) ../Ger....... Badische..... VI | 765,079. 
Winter, Poetigts i... ence esses Ger. ceces Hochst......- VI |697,765. 
Winter, Friedrich M. ......... Gf. ccs do eee ees esaeres XXIII | 905,264. 
Winther, Adolf, August L. Las- 5 : 
ka and Arthur Zitscher ..... Ger....... Griesheim....| VI | 1,034,853. 
Felix Kunert and Edwin } ; 
EE Re Sa ae (er Griesheim....| VI | 1,099,108. 
WA PR ESTUIRE cuca ioe ces ce ses 0% ee er Cree co eee XXII | 685,895; 714,428. 


Chem. Found.| XXII | 1,339,310. 
Wise, Louis E. See E. Q. 


dams. 
MV ISPAENIOTTIS, crises cose sss N. Y..... Jere cere seeee XXI |221,381. 
Witt, Otto N. (see H. Koech- y 
SN ees, iets os ss Ger....55. Badische. ...| Yr |381,045; 381,046; 420,372; 
420,374. 
G@assellaunie. V 248,246; 249,136; 
XXII | 420,373. 
XXIII | (Az) 1,093,567. 
WoiterttGeG icc. i.e. cay, Elberfeld....- VI |761,1235 791,524; 791,525; 
791,526; 842,048. 
eS Ger... .ceefeerr steer: XXII | 710,648. 
Wohlfahrt, Theodor. See M. 
Bazlen. 
Wolfes, Otto and Horst Maeder|Ger.......J-e-setseeere XXIV | (m) 1,419,092. 
oe ie Sere ect a Swit7ise ee |cumoe ous se VI |389,127. 
olff, Hugo (see O. Bally, : f 
BH. later a R. Just) Pee \Ganls. oe: Badische..... III |893,412; £95193: 1,063,000; 
1,133,081. 
XV |1,054,888; 1,061,714. 
and Filip Kacer ......... Gee cits Badische..... III | 1,266,896. 
foie 92 CC. N. Y..... {Albany An... II 189,538. 
and Ralph Bertley ........ Rage ae TIT | 188,217. 
VI_ |277,182; 285,335. 
Wolffenstein, Richard ......... eT ae eae: tee e eee XXIV |(m) 1,063,099. 
and James Colman ....... erie: Berlin....... XXIII | (Ab) 1,019,576. 
Wollenberg, Harry L. ........ Wo aes 
and C. A. Bigelow ....... NiNi oc. . PCa ers sae. XXIV | (e) 1,297,524. 
Wollenberg, Waldemar. See R. 
Miller. 
Woltmat GC0WIk. occ acc ccase Ger neues Elberfeld..... DLE 72,S57. 
Payer a) vers: III |935,878. 
Wolpert, Ernest. See E. Hepp. 
Wolvekamp, Mari E. ......... Tee ae Abbotts eater XXIV |(m)1,361,128; 1,412,440. 
Woodbury, Clifford A. ........ iif eee ee da Pont... ++ XXIV | (e) 1,309,559. 
Woodruff, Theodore T. ....... Eee A ene Morris (%)..| XXIII | (In) 126,663; 126,664. 
Vee Se ET i oa | C: ee Héchst..... . | XXIII | (Su)907,937. 
Wray, Edward (see K. Elbel) . Ene Sarviers« Clauss. .casss XV_|1,247,475. 
re nee Kalle; 2.02.2.) VIL. 11,108,056;5" 1,108:087; 
; 1,157,485. 
and Fritz) Peso ......+.-0> Ger. iiss: Wales ee VII | 1,144,577. 
UE, St | a res OTe e dns Hachette 55: VI |{1,056,080. 
(URN TEMNED Tiaig Dele iaiyse views os 0 ae GELo ciwisse's Hochst......- vI 1,154,826. 
Wiirgler, Jakob (see A. Grob 
_and G. Engi) ............ SwitzZic-. + | Raslew. 2s ee XI | 1,227,407. 
DM URERNCT MIT fc ccc cesses (Gere. Gieglest. oak ve XXIII | (Az)918,244. 
Wuth, Berthold and C. Jager- 
SE OE RE aoe pn a cs 0.4 vse « SWitzi.cns 4 Basledwo.. VIP® | 1,216, 8t2ecer. 2s saa3e 


1,234,994; 1,216,760. 
Eugen Anderwert and B. : 4 4 
CEES ine < és aces ne ssa'ss Witte. ss BasleGios cae VI 11,216, 760. 


576 


DIGEST OF PATENTS 


—————CC“LlllIl]lIl]_——sSss——ss—_—_—_—__S__=_S__=[=[=[[=[{j{aqa{=_={a~=—a=]E|[{=—=e={—=azEzqaEx{E—Eq{]{_—@_@_=[ee{{™{=x7xx=x=x=*=*=€#€—_c_=€—*{X{”__][=[=][[[S—[{_===a=_==@ 


COUNTRY 
PATENTEE OR STATE ASSIGNEE 
Wypbert, Ernst. See A. Gans 
and M. Hartmann. 
Wyler, Max (see H. Levinstein)|Eng...... Levinstein... 
; British Dyes. 
Yarnall, Elizabeth S. ......... Morn tos ee cee eee 
Zacharias, Emil and Eugen 
Bernhard sop weve leeiieaiies cvwte Gef. . <i 20 Griesheim.... 
Zart, Arthur (see IL. Hesse,|Ger.....-- Bayer: 6. ones 
O. Gunther, A. Ossenbeck, K. 
eae and H. Schweitz- 
er 
and Hugo Schweitzer ..... Geren peaks Synthetic..... 
Zechentmayer, K., and O. 
Stachilin oy src cites is cls siccvetelacs erie (TOTS guekoes EPGCHST. cannon 
Zedel, Wilhelm. See N. Schwan. , 
Zehntner, “Ernst lives coat eee: Switz... Durand.....- 
(see C. de la Harpe) 
Zeltner, J ohanns %..c. tienes sie0 ss Bavariat.leceses tates 
Zengeler, JON cs. .cicwsles sins Me de Re's 13.2 VNtoarae ha ee 
ZOENEL, / TUENGE Vin gine des ve me a eee ATES wilh oles ehLaeibeee 
Ziegler, \HENnry. ssc bows es cscs GOL as glee © Badische. .... 
Liemler;  JOREE Cones vies sic'sa a sta s SOPs hb six nes Fritsche. ....; 
Lembach..... 
Zingg, Adolf. See H. Zueblin. 
Zinkes PAOIs Poa sista eae toes sats Nays tories Pereira...... 
Zinssmann, Emil ©... .0..6604s> N. Y..... |Rumpff (14) 
Zitscher, Arthur (see A. Win- 
ther and A. lL. Laska) .....; Ger..... Fie) (eure yp wear Joe 
and Ernst J. Rath Geriteades Griesheim.... 
Felix Kunert 
and Edwin Acker ...... Getiandes Griesheim.... 
Zollinger, Ernst H. and Herman 
Roebling y 3 tres sacs s arse eres GEL dis sed (Glo ahe eaeeaton ts 
Lollner, ieMene” saca hy sae aa eo Get,; save Chem. Fab... 
Zublin, Heinrich and Adolf 
ZING a ower os ates eote sy Vier aeys Ltalviaee Schlaepfer. . 


vil 


XXII 
vI 


PATENT NUMBERS 


1,358,490. 
1,467,598. 


846,887. 


675,434. 

999,944; 1,001,183; 
1,012,960; 1,015,375 
1,022,287; 1,022,288; 
1,032,797: 

1,114,844. 


(Ni) 1,031,823. 
1,075,134. 
207,093; 207,836. 
90,417. 

1,436,136. 
324,630. 

(m) 563,116. 

(m) 466,708. 


1,454,204; 1,454,205. 
(Tr) 76,031. 


1, LOT, TEts 
1,028,521; 1,066,777. 


1,122,564. 


11350, 472. 
(m) 1,086,881. 


(Az)601,420. 


a 


SCHULZ INDEX. 


This index is arranged in the same order as the 1914 edition of Schulz’ “Farb- 
stofftabellen,’ and the census of dyestuffs, 1913, “Artificial Dyestuffs Used in the 
United States,” by Dr. Thomas H. Norton. The names are those first mentioned 
by Schulz. For a complete alphabetical name index of dyes, reference is made to 
either of the above works.* Patents corresponding to some Schulz numbers have 
not been filed in the U. S. Patent Office, and some patent numbers in Schulz were 
found to be incorrect. 

Numbers in ttalics are patents of homologous or closely related dyes and are 
indicated in the abstracts by words “Near” or “Homolog of” preceding the Schulz 
number. Further references at the bottom of each abstract will also aid in the 
location of dyes closely allied to those reported by Schulz. Mineral and vegetable 
dyes have been omitted in this index, as there were no corresponding patent numbers. 


N ba 
= Fs NAME | Patent No. 36 NAME Patent No. 
By4 Bis 
n 
Group I.—NITROSO. (Abstract, Group X.) 
tieolid Green O........ | | FUR eicdadd ee gias'e x | 
BOGAN oh ape ede ss 4|Naphthol Green B ...] 316,036; 362,835. 
Group II.—-NITROSO. (Abstract, Group IX.) 
Oa aS ee 300,874; 666,627; 6|Martius Yellow ...... 
1,200,171; 1,349,802; 7|Naphthol Yellow S ...| 225,108; 289,543; 
1,380,186; 1,396,001; ; ; | 324,615. 
1,413,914. 8|Pigment Chlorin GG .} 763,756; 955,080; 
Group III—STILBENE. (Abstract, Group XIV.) 
ojSun Yellow ......... 360,553. 14|Diphenyl Chrysoin G .| 951,046. 
10o|Mikado Yellow ...... 15|Chicago Orange G ..| 601,063. 
11|Mikado Orange ...... 395,115; 396,527. 76/Curcuphenine "2. .....- 951,046; 951,048. 
12|Diphenyl Citronin G .| 613,911. 17|Chlorophenine Orange. 
13|Polychromin B ...... 455,952; 636,065. 18|Diphenyl Fast Yellow. 
Group IV.—PYRAZOLONE. (Abstract, Group XII.) 
19|Flavazin L .........-. 24|Pigment Fast Yellow R| 935,370. 
BOVPIAVEEIN GS ci ve sw sens 25|Dianil Yellow 3 G ..]| 658,593; 662,056. 
21|Pigment Chrome 935,829. 26|Dianil Yellow R ....| 656,857; 679,172. 
PINS ciple os we ss 27|Dianil Yellow 2 R ...| 656,858; 656,859. 
22|Xylene Yellow 3 G ...| 901,675; 982,050; || 28|Pigment Fast Yellow G| 731,670. 
984,900. 29|Eriochrome Red B ...| 808,919; 1,026,257. 
23 TAGtlazin 2 ce cdesas 324,630; 627,690; || 30|/Radial Yellow G .... 
935,830; 969,428; 
972,951; 1,010,919; 
T,096,600 ; 1,447,485. 
Group V.—AZO. (Abstract, Group VI.) 
Amidoazobenzol ...... 27, \Ovang Gn lug nests 
37 \ Butter Yellow ......- 48|Alizarin Yellow GG...| 424,019. 
33(Chrysoidin ........++- 49|Prague Alizarin 
34|Chrysoidin R ........ 221,120+ Yellow G ......005. 528,965. 
35|Sudan G .....+eeee- 50|Azo Cardinal G ...... 
36|Sudan I .......--+-- 51|Nitrophenine ......... 
37|Ponceau 4 GB ......- 52|Archil Substitute ....| 211,525. 
38|Orange G .....------ 251,162. 53|Archil Substitute 3 VN} 380,928. 
39|Ponceau G, 2G ..... 251,162. 54|Apollo Red B, G ..... 376,392. 
40|\Chromotrop 2 R ....| 458,283. 55|Brilliant Archil C .... 
41|Fast Acid Fuchsin B. 56|Paranitranilin Red ...] 211,525; 598,118; 
42|Amido Naphthol Red G 601,420; 724,743; 
43|Tolan Red B, G ..... 563,383. 728,388; 728,455. 
44|Azo Archil R ........ 57|Chromotrope 2 EAA) Paeebekeer 
45|Brilliant Lake Red R . §8|Alizarin Yellow R ....] 431,297. 
46|Metanitranilin Orange.! 557,228. 590|Wool Violet S .....- 525,656. 


* A more complete list of names of dyes may also be found in the Colour Index, published 
by the Society of Dyers and Colorists. This work is so thoroughly cross-referenced to the 1914 
edition of Schulz that no difficulty can be experienced in using both publications in conjunction 
with the digest of patents. 


NAME 


Grove V.—(Continued).—AZO. 


~60|Azo Phosphin GO ....| 626,913... ~~*{| 128|Janus Gray B, BB ..| 613,920. — 
61|Victoria Violet 4 BS. 
62|Azogallein . 3... tse. 
63|Azo Acid Blue B .... 
64|Azo Acid Red B ..... 
65|Azo Coralliny Loic... s 
66|Amido Naphthol 

1 Red? Gas oct s as 
slChneuetrade OB rere 
68|Spirit Yellow R ...... 
69|Chrysoidin Rss... +s 
70|Brilliant Orange O . 
71(Azo Fuchsin Bo...) .; 
72|Pigment Orange R ... 
73|Pigment Fast Red HL 
74|Tannin Orange R .... 
75|New Phosphin G .... 
TOV Oud a ce Late sicele as heiibe 
77\|Azo Coccin 2 R ...... 
78|Cochineal Scarlet 4 R. 
79|Brilliant Orange R ... 
cg ithe Scartet Roo Fst; 


sri pautin Scarlet Attn: 
$2) Ponceau e2u kk veces cre 
83|Ponceau 3 R, 4k. 
84| Azo Chromin ..... arene 
85|Omega Chrome 

(oi DISCICURN tac oc a tae. 
BOUACErIN, Oto. «+c sh. els 


87|Peri Wool Blue Bo Ae 

88|Acid Anthracene 
{SOTO WH Gk Aes ae Serene 

89|Metachrome Brown B. 


90/Chrome Brown ...... 
91|Anthracyl Chrome 
CsreenmeAtrocs oe cet “ 


deaux R 
OF sudan Ramee Scene ee 
94|Azo Eosin G . 
95|Azo Cochineal ....... 
06 Chrome Fast 
Yellow GG ....08. 

07|Chloranisidin Scarlet . 
98|Naphthol Rose ....... 
99|Tuscalin Orange G . 
Z00|osamin (Be... = eee 
go1!}Coccinin (By On... oe 
102| Diamond Flavin G. 
103|Holland Yellow 
104|Benzoyl Rose ....... 
tosjsudan Brown ....... 
106|Carminnaphth Garnet. 
107|Sulfamin Brown A . 
108|Double Ponceau R .. 
109] Palatin Red. A... 2. 
110/Buffalo Rubine ...... 
113 | Fast. Réed (BR oh is, 
ri2\ Fast Red -B Se 2.0. 
113|Crystal Ponceau ..... 
114|Chromotrope 10 B . 
115|Azo Turkish Red .... 
116|Sulfamin Brown B .. 
17 erika eG Noah cee 
118|Geranin 2.B, Gils... 
119|Diamin Rose’ Re eee, 
120|Salmon: Réd.... 20.00% 
rc Brika Bary er aeeo 
2g rika Goes) eee eae 
S25 Rinna Red ee cate ek 
124|Diazin Green S ..... 
125 Diazin Blackwwevaloene 
126|Indoin Blue R ...... 
127|Methyl Indone B, R. 


DIGEST OF PATENTS 


Patent No. 


626,913. 
792,032. 


567,615. 
7975732. 


941,088, 
718,181. 


217,071: 
466,841; 
500,761. 


515,100. 
515,100. 
201,671; 
268,113; 
268,113. 
268,113. 
268,113; 
456,627. 
268,113. 
210,233; 
251,163; 
548,460. 
841,371. 
302,790; 


306,546; 
827,468. 


657,064; 
658,507. 
987,362. 
664,055. 
704,825; 
213,564. 
213,563. 


695,812. 
982,952. 
945,780. 


204,799. 
204,799. 


204,709. 
251,164. 
332,528. 


911,185. 


535,037. 


418,657. 


524,251; 


468,142. 


268,113. 
456,897. 


333,035; 


268,113. 
268,113. 


303,335; 
306,969. 


657,065; 


704,826. 


524,252. 


NAME 


(Abstract, Group VI.) 


128| Janus, Gray 1B, 3B Be 
129|Chromazone Red ca oo 
130|Chromazone Blue R . 
131|Permanent Orange Be 
al ee Red By vaverereisvets 
133|Eriochrome Phos- 

Din ptvieeesy. ele aie ae 
134 Metanil Yellow ...... 
135|Brown Metanil Yellow 
136|Acid Yellow MGS .. 
137| Fast, Yellow Geis. => cise 
138|Helianthin 
139 |Orange) LV it. se sree 
tTa0\Azohavin RS) a eee 
141|Azo Yellow 3G ..... 
142|Brilliant Yellow S . 


| 
| 
ae 


eeoeeeseeres 


144|Orange I. o.cse see 
1745 |Orange lI. ances 
146|Azo Fuchsin G ...... 


147|Azo Fuchsin 
148|Fast Orange O ...... 
149|Fast Yellow Y ....... 
150|Fast Yellow N ...... 
151|Orange T oe 
152|Lithol Rubin B ..... 
lens Red: Cis caries 


| 
154]Acid Alizarin Brown B 
155|Acid Alizarin Garnet R 
156|Acid Alazarin Violet N 
157|Diamond Black PV .. 


158|Chrome Brown RR .. 
Ebi a> Alizarin Black R 


160|Naphthylamin Brown. 
161| Fast Red Anjan ee 
162|Brilliant Fast Red G . 
163|Azo Rubin .....00seae 
164|\ Fast (Red (V Ries tere 
Azo Red) Avaee cesenet 
1661 Fast] Red) Ey yayee eee 
167|Crocein Scarlet 3 BX. 
168| Amaranth 
169|Cochineal Red A ..... 
170|Ponceau 6 R ........ 
171|Chromotrope 8 B .... 
172|Fast Brown 3 B ..... 
173) Lithol (Red Roose 
174|Double Brilliant 
|. Searlet. /..5:0.nenenenee 
175|Ponceau for silk, G .. 
176|Double Scarlet Si eee 
177|Chrome Yellow D ... 
178|Crumpsall Yellow .... 
179|Lake Bordeaux B . 
180|Eriochrome Blue 
Black? Bii.s%. anes 
181|Palatin Chrome 
Black:'6:=Bo ex vives 


182|Fast Sulfon Violet ... 
183|Eriochrome Black T . 
184|Eriochrome Black A . 
185|Anthracene Chrome 

|. Black (chop eeareeene 
Lanacyl. Violet Biize.. 
187|Lanacyl Blue BB .... 
188/Tolyl Blue SR ...... 
189|Sulfon Acid Blue B . 
190|Alkali Brown ........ 
Pyramin Yellow R .. 
Cotton Orange G 


165 


186 


IQI 
r27 srethy! tndone DB. KR...) ite 192|Cotton Orange Go epee o ee 


Patent No. 


613,920. 


688,647. 
714,882; 
932,289. 


991,750. 


210,054. 
253,598. 
210,054. 
210,054. 


210,054. 
210,054. 
210,054. 
466,841; 
833,605. 


714,883; 
253,598. 


741,020; 
733,280; 
759,716; 
983,486. 
628,814; 


692,675; 
727,967; 
548,460. 
654,064; 
667,935; 
741,552; 
204,799. 
204,799. 
204,799. 


204,799. 
256,376. 


314,938. 
268,506. 


332,829. 
650,757; 


332,820. 
690,294. 
332,829. 
555,058. 
858,065. 
806,415; 
779,177; 
790,364; 
640,989. 


790,363. 


656,120. 
524,262. 


921,239; 


468,142; 


888,981. 


743,071. 


752,562; 
765,080; 


647,230. 


727,962; 
729,001. 
654,065; 
672,714; 
933,842. 


718,356. 


835,539. 


778,476; 


807,422. 


NAME 


Schulz 
No 


Group V.—(Continued).—AZO. 


193|Clayton Cloth Red ...| 404,097; 
194|Rosophenin 1o B .... 
195|Rosophenin SG ...... 398,990. 
106, \itan Rose 3 B ...... 
197|Thiazin Red G ...... 398,990. 
198|Clayton Yellow ...... 428,629; 
446,009. 
199|Oriole Yellow ....... 398,990. 
zoo;wake Red D......... 878,964. 
201|Pigment Scarlet G .. 837,128. 
202|Acid Alizarin Red B .| 757,109. 
203| Yellow, soap fast ....} 297,852. 
204|Diamond Yellow G .. 
205|Diphenyl Chrysoin R R| 644,462. 
206|Diphenyl Catechin G .| 644,462. 
207|Diphenyl Fast Brown 
Ev ECan a 644,462. 
208|Leather Brown ...... 
200\lérracotta F ........ 440,288. 
2z10|Cotton Orange R ....] 524,261. 
211|Resorcin Brown ..... 260,359. 
212|Fast Brown G, GR ..| 741,936. 
233iFast Brown .:....... 
214|Fast Brown O, NT 
2rsipiie Black Noo... .. 563,384; 
216|Domingo Blue Black B| 606,438. 
217|Naphthol Blue Black S| 480,326; 
BG NIWWTOphOr 2), 6s ae as 
219|Chrome Patent 
COTREHOIN a Su hectic 
220|Palatin Black A ..... 590,088; 
683,120. 
221|Anthracene Acid 
AS TOMER Wrsiieie.6 wie tower lol's 
222|Janus Yellow G, R ..| 623,697. 
Poe iol hee)? 
224jCioth Red G’........ 
Zaeierocemm AZ: ........ 
O20 Crocein “Bis. vac... 333,0375 
227|Brilliant Crocein M ..| 233,465; 
228|Ponceau 5 R ........ 268,507. 
229|Azo Acid Violet ..... 
230|Cloth Red 3G ...... 
agree Red 3B ....... 
Sepp MtIeE Vi hi Ss. es as 
233/Cloth Red B ........ 
aga; clote ned G........ 863,396. 
BES TOCOIINS Bo oc euis ese 333,035. 
asoi\Cloth Red B ........ 578,432. 
gaol mordeaux BX ..../.... 
238|Union Fast Claret ...] 246,221. 
2aolice Black ..........; 586,865. 
240|\Janus Red B ........ 623,697. 
241|Neutral Gray G ...... 
242|Sulfon Black G, R ...| 498,404. 
243|Coomassie Wool ..... 
PEIRCE ERE 6 6 coal « v0 654,167; 
244|Coomassie Wool 
OU 654,167; 
245|Nyanza Black B ..... 491,410; 
52,107. 
246|Cloth Scarlet G ..... 
247|Double Scarlet ...... 224,927; 
246) Past Scarlet B ...... 224,927. 
249|Crocein Scarlet ...... 256,378; 
250|Milling Orange ..... Pa 
251|Crocein Scarlet O ... es 
2sz2iCloth Searlet R ..... : 
B2ss/Orsetllin BB ........ 
254|Bordeaux G ......... 
255|Crocein Scarlet 8 B ..| 256,375. 
266) Sulfon Black ........ 
257|Sulfon Cyanin G .... 
258|Naphthalene Acid 
By a ge lee sae aTa)'oh 
Sroeonceat 16 RB ..\...< Rie LO, 
260|Eriochrome Verdon A 
261|Buffalo Black 10 B ..} 618,963. 


Patent No. 


SCHULZ INDEX 


NAME 


No. 


(Abstract, Group VI.) 
Victoria Black Bee. a. 


441,945. || 262 


203) etm lackn Ramrauitesene« 425,885 
264|Fast Sulfon Black F . 
265|Sulfon Cyanin Black B 
266|Naphthylamin Black D} 412,440. 


440,281; || 267|Anthracite Black B ..] 502,912. 
268|Naphthyl Blue Black N 
269|Naphthol Black 6 B ..{| 345,901. 
270|Brilliant Crocein .... 
271|Diamine Blue 6G... 
272|Naphthol Black B 345,901. 
273|Diaminogen Blue BB . 
274|Diaminogen B ....... 533,463; 

29,74 
275|Diamond Black F ...] 438,438. 
276|Diamond Green B . 438,438; 
277|Anthracene Acid Black 
278|Biebrich Patent Black] 476,070; 
546,069; 
279|Benzo Fast Scarlet .. ia oie 
97,705; 
280|Azidin Fast 
Scarlet} GGS-7 45... 
281 cater! cl en 
Garlel de Does saan 
$23,058. 282 wet Fast oe: 
cafletyp ison. ses 

557,440. 283|Bismarck Brown ..... 

BOA WIESU Viti ee Liauemeteretett mes 
285|Toluylene Brown G ..| 516,380. 
593,790; 286|Toluylene Yellow ....] 568,540. 
“*"" || 287|Toluylene Orange RR] 497,032. 
288|Acid Alizarin Black ..| 665,696; 
692,676; 
289|Acid Alizarin Black ..| 677,227; 

290| Violet Black ........ 
291|Azo Alizarin Bordeaux] 631,089. 
292 Sane as Ailes I .| 628,721; 

_ || 293| Milling Red G ....... 

er heey 294|Anthracene Yellow C. 
295|Diphenyl Fast Black .| 525,245; 
296|Cotton Yellow G..... 430,535. 
297|Benzo Fast Rose 2 BL| 678,323; 
298|Milling Red R ....... 
299|Cinnabar Scarlet BF . 
300/Cotton Ponceau ..... 
301|Hessian Purple N ....] 350,230. 
302|Brilliant Hessian 

Purples. eee ee 350,230. 
303|Brilliant Yellow ..... 350,229 
304|Chrysophenin G ..... 395,115 
305|Hessian Yellow ...... 350,229 
306|Pyramin Orange 3 G .| 631,610 
307|/Congo Red .......... 365,667 
308|Diazo Black B ....... 
309|Glycin Red .......... 

654,168. || 310|Glycin Corinth ...... 498,303. 
sii~Orange TAs ockaees 

654,168. || 312|Congo Corinth G ....| 344,971; 

511,688; || 313|Congo Rubin ........ 
314|Pyramin Orange RR .| 631,611. 
315|Congo Orange G 454,840; 

224,928. || 316|Brilliant Congo G ... 

317 Eiiemidel own BG.| 361,404. 
318| Benzidin “Puce |... 35 bees ecers 
ene 219| Diamitz Scarlet Bo...’. | 2 426,945% 
9° 9 9 9 tb go] Bordeaux CGV 0,.,2,)6¢ © 2 > 
2 oe oo 32 Sboliotrope 2°32..." 
322|Trisulfon Violet ..... 584,981. 
323|Dianil Blue R ....,,. 


4 324(Chicago Blug 4 R .2 9). 
; » 325 /Columbia Biyre Ro es 
‘ 426 0Oxamin >Yiolet 22.2.2..7 527,090; 
327|Diamin Violet N .... 
328|Diamin Black RO ... 
329|Diamin Brown V .... 
320|Zambesi Brown G, GG 


579 


Patent No. 


560,796; 


464,775. 


546,068; 
546,070. 
663,498; 
1,015,375. 


677,231; 
693,670. 
680,283. 


640,010. 


575,904. 
687,171. 


358,865. 


563,384. 


724,893; 


eer a ee ee en ne ee ee an 


580 DIGEST OF PATENTS 


N 
3 NAME Patent No. 36 NAME Patent No. 
52 Sz, 
n 
Group V.—(Continued).—AZO. (Abstract, Group VI.) 
331|Alkali Dark Brown GV| 611,111. 400|Milling Scarlet 4 R. 
332|Dianil Garnet B ..... 842,048. 401|Diamin Blue 3 R ot 380,067; 588,203. 
333|Diamin Black, BH ...] 501,500. 402|Diamin Blue Black E. 588,203. 
334|Diphenyl Blue Black . 556,164; 567,413. || 403|Diamin Black BO . 442,369; 588,203. 
335|Naphthamin Black RE 563,386. 404|Diamin Yellow N ....]| 308,067. 
336|Benzo Cyanin R ....| 499,198; 533,508. a Benzopurpurin 10 B .| 357,274; 481,934. 
337|Diamin Blue BB ..... 464,135; 544,699; 6\Diazurin ib eo. eae 
544,700. pi Azo Violets)... Gann’ 447,302. 
338|Naphthamin Blue 2 B.| 563,385; 563,386; || 408|Dianisidin Blue ......] 525,492; 569,392; 
606,181. ; 575,228. 
339| Brilliant Orange G .. 409|Trisulfon Blue B ...| 584,981. 
340|Benzo Orange R ... 447,303. 410|Benzoazurin G ...... 481,934. 
341|/Crumsall Direct Red.. 447,303. 411|Benzoazurin 3 G..... 357,273; 388,185; 
342|Chrysamin’ G: 0). 3..34 320,638; 329,630. 481,934. 
343|Diamin Fast Red F .. 412|Congo Biue'2 B yess 467,162. 
344|Diamin Brown M ....]| 535,036. 413|Direct Violet BB ....| 524,060. 
345|Oxamin Maroon .....} 558,344. 414|Indazurin B_........ 524,069. 
346|Oxamin Red ........ 555,359; 666,867; || 415|Dianil Blue G ....... 
679,974; 724,894. || 416|Brilliant Azurin 5 G . 
347|Diphenyl Brown RN .| 567,413. 417|Chlorazol Blue B ... 
348|Diphenyl Brown BN .| 567,413. 418|Diamin Brilliant Blue 
349|Diamin Brown B .... Ge. wa eee 512,493; 532,1255 
seal Alkalt Yellow R ..... Wal 535,037. 
351|Cresotin Yellow G ...| 394,841; 396,294. |] 419|Chicago Blue RW ... 
352| Direct WVaolet Ri. 527,070. 420| Azidin Wool Blue B . 888,036. 
253|Direct Indigo Blue BN| 525,626; 536,878; || 421|Oxamin Blue B ...... 558,344. 
557,438. 422|Chicago Blue 4 B ... 
354|Direct Gray R ...... 493,504; 525,626. || 423|Chicago Blue B ..... 
355|Anthracene Red ..... 493,583. 424|Chicago Blue 6 B ....| 511,532. 
356|Dianol Red 2 B..... 594,123; 625,174. || 425|Benzocyanin 3 B .... 533,508; 578,432; 
sesiDianct Li Wh <a ee aeLes 594,123. 1 A 603,008. 
358|Brilliant Dianol Red R| 594,123. 426|Diamin Pure Blue ...| 464,135; 498,874; 
350) Trypan Red iso. k ken : 521,986. 
360|Pyramin Orange R ..| 545,333. 427|Indazurin GM ..... +| 524,070. 
36r/Sulfon Azurin D ....| 432,989; 499,216. || 428|Direct Blue B ....... 493,563; 620,368. 
362!Toluylene Orange R . 429|Indazurin BB ....... 524,070. 
363!Benzopurpurin 4 B ..| 329,632; 416,145; || 430|Indazurin 5 GM ..... Sea G7e- 
420,350. 431 Diamin Gold Yellow .| 472,121. 
364|Benzopurpurin 6 B .. 432|Diamin Catechu ..... 359,576; 464,566; 
365!Benzopurpurin B ....| 329,633. ; 473,928. 
366|Diamin Red B ...... 433|Coomassie Black B ..| 629,748; 634,009. 
367|Diamin Red 3 B.... 363,502; 375,848. || 434 Coomassie -Navy Blue.| 629,748; 634,009. 
368|Brilliant Purpurin ... 435|Janus Brown B, R ..| 602,637; 602,638; 
369|Brilliant Purpurin R .| 468,539. ‘ 602,639; 602,640; 
370/Brilliant Congo R ... 610,345; 623,697; 
371/Rosazurin G ........ . 626,913; 1,000,606. 
S72) Rosazntin be ee 381,132. 436|Columbia Black FB ..| 526,763; 679,221. 
373/Congo Orange R 437|Isodiphenyl Black R .| 615,407. 
374I\Congo 4 R...... bts 438|Melanogen Blue BH .| 501,616. 
a7<iCongo Corinth Bo... 439|Direct Indigo Blue A.| 536,878; 557,438. 
IP p : 
aed lhe ae age aaa 366,078. 440|Direct Indigo Blue BK 
378!Trisulfon Blue R ....| 584,981. 441|Diazo Blue Black RS .| 482,106. 
379|Diaml Blue 2 R>. 442|Direct Black V_...... 601,033. 
38e(Dianil’ Blue Boon. 443|Direct Indone Blue R| 601,033. 
Leb ne: Black Blue B, R| 468,040. ah Cope boa ee: 
382!Azo Mauve B ....... poe neal 462,824; 445 Crumpsall Direct 9 
282!Naphthazurin B ..... 608, ; Brown O ....... «+ 622,065¢ 
384!Chicago Blue 2 R'....| 888,036. ppratbemarrrnde i 479,515. 
285|Oxamin Blue 4 R ...|{ 521,095. 448|Diarnt Bee Gin 476,393; 503,148. 
384!Diamin Blue BX ..... 498,873. 449/Trisuifon Browa B cite aad 
387|Columbia Rlue G . ceo Bene BI k Blu Rr. 608,024. 
338] IeHicee Blue TR wc... |, $26,284; $09,929. pie chao Sant Blue Bt 
39" Ebol: | lue B oa re bac) +} Shores O06:4273 § 452|Renzo Indigo Blue ..| so1,118; 602,856. 
Pe Shanice st ae ‘|-453f Colustbid ‘Black R .++| £76,604, 
3901 Benzbéyaain: Bi woe < 333,503 5 ‘5783423. 4) 454|Trisutfon: Brown G ..| 608,024. 
391/Diamin Blue 3 B ... 521,985. 455|Columbia Black B ... 


392| Toluylene Orange | Cie -| (375,930; 395, 634. 45.6|Congo Fast Blue B .. 
Sas tDiohedy Brown 3 GN 5875413. ce 2 |. 45%|Trisulfon Brown GG .| 608,024. 


394|Chrysamiay Re x. 8 iy 329.6487, “Aor, 0242 452] Carbon Black | Gene 
395!Cresotin Yellow R' ‘ 364,8115 «<<< « » |h4g¢|Benzo Black Blue G . 
396|Indazurin RM ....... 524,070. 460|Benzo Black Blue 5 G 
397|Direct Blue R ....¢.. 493,504. 461|Coomassie Union Black} 619,104. 


398|Direct Gray B ...... 462|Erie Direct Black GX.| 515,381; 688,478; 
3golIndazurin TS .......) 524,070. Ne 


SCHULZ INDEX 581 


N N 
Z Pe) NAME Patent No. iS 3 NAME Patent No. 
4 OG 
mn 2 
Group V.—(Continued).—AZO. (Abstract, Group VI.) 
 463|Erie Direct Black RX.| 688,478. 478|Columbia Green ..... 
464|Erie Direct Green ET.| 688,478. 479|Dianil Black R ......] 582,958; 582,959. 
465 cy ne Black 480|Congo Brown R ..... 572,723. 
Gre Dre sal e's ‘aviovuite 481| Azo Corinth Giceocss sc» 516,381. 
466 Eboli ae CW, "etc.. 606,436; 606,437; || 482|Alizarin Yellow FS .. 
606,438; 606,439. || 483|Rouge de St. Denis ...}] 483,368. 
467|Diphenyl Green ......| 628,233. 484|Milling Scarlet B ....] 483,368. 
468|Diphenyl Green 3 G..| 628,233. 485|Benzo Brown G ......] 384,315. 
469|Chloramin Black N .. 486|Direct Brown J .....| 491,422. 
470|Chloramin Greeen B..| 627,679; 652,456. || 487|Benzo Brown B ...... 
471|Chloramin Blue 3 G..| 652,456. 488|Toluylene Brown R ..| 465,116; 683,190. 
472|Chloramin Blue HW.. 489|Hessian Brown BBN.. 
473|Diamin Black HW ... 490|Cotton Brown A, N.. 
474|Diamin Green B .....| 628,233. 491|Dianil Black PR ....| 576,203; 578,580; 
475|Diamin Green G ..... 514,599. | 644,292; 832,393. 
476|Benzamin Brown 3 GO 492|Anthracene Acid 
477|Congo Brown G .....! 399,581. BEownu. Die comes «cot 


Group VI.—AURAMIN. (Abstract, Group IV.) 


AGP OMTAMIN 5 ccxcmwsovsse| 301,802; 720,920. 


so4| Sura Gre wegsecenel -Q0S,A30) 


Group VII.—TRIPHENYLMETHANE. (Abstract, Group XVIII.) 


495|Malachite Green ......| 222,257. 535| Methyl Alkali Blue ... 
496|Setoglaucin O . 536|Alkalt Blue R, B..... 
497|New Solid Green fs 3B 537|Methy! Blue for Silk .| 333,86r. 
498|Turkish Blue B, BB . 541,572. 538|Methyl Blue for Cotton] 538,215. 
499|Brilliant Green ....... 539|Water Blue ......... 538,215. 
-500|Setocyanin O ....... ; 540|Pacific Blue ......... 
sorjGlacier Blue ......... 525,627. 541|Brilliant Dianil Blue .. 
502|Guinea Green B ..... 542|Agalma Green B ....| 886,815. 
503|Night Green A ...... s43iPatent Blue V ......1| 432,613; 412,614; 
so4|Light Green S F, | 412,615; 519,971; 
Gls SS eae 266,912. | 647,834. 
5s0s5|Light Green S F, Baa CYaTIM TD) scala Sate ao ee 463,898. 
oS ee g45\Patent, Blue A ..<ss-| (4%2;6533,> 412,613 
506|Erioglaucin A ....... 564,801. 412,615; 422,018; 
507|Xylene Blue VS ..... 538,027; 709,160; 567,567. 
| 731,139. 646/Cyanol FR acco. 8 .-| 472,091; 567,567. 
508|Xylene Blue AS ..... 583,267; 615,485; || 547|Ketone Blue 4 BN .. 
| 673,632; 731,139. || 548| Acid Violet 6 BN ...] 501,434. 
so9|Chrome Green ..... ..| 502,104. 549|Chrome Violet ....... 476,414; 478,005; 
sroj|Azo Green .......... . | 501,104. 
s11|Para-fuchsin ......... 550|Chrome Bordeaux .... 
Sia/Puchsin ............. 50,335; 53,241; || 551|Eriochrome Azurol B.| 877,053; 887,620; 
2AS,1543 6252,202% | 950,359; 978,800; 
283,766; 310,128. || | | 999,028 ; 1,042,493; 
513|New Fuchsin O ......| 47156383 473,453. | 1,244,149. 
SravRemevaolet S Ro oiee ss 43,066. 552|Chromate Blue G ....| 877,054; 980,251; 
315|Methyl Violet .......| 325,828. Riel 999,028; 1,042,493. 
516|Crystal Violet .......| 299,856; 290,801; || 553|Eriochrome Cyanin R.| 877,052; 947,876; 
290,892; 329,636. 999,028 ; 1,042,493. 
517|Methyl Violet 5 B....| 297.415; 297,416. ||554|Chrome Azurol S ....] 877,054; 999,028; 
518|Ethyl Violet .........| 299856; 290,891; | 1,042,493. 
290,893; 325,827; ||555|Aurin ...... Bangee cs 978,799. 
329,637. 556'Red Corallin .........| 307,40%; 316,471; 
s519|Methyl Green ........ | 318,484; 333,649; 
520|Light Blue, spirit sol..| 252,203; 327,953. | 589,766; 591,309; 
g21|Spirit Blue .......... 32,965; 248,153. | 609,598; 995,494. 
522|Victoria Blue 4 R....| 308,748. 557|Chrome Violet .......| 410,739; 603,300; 
523|Fast Green, bluish ...| 4233413 498,471. ber cies 609,599. 
Sea, Pucesin 5, SN ....... 250,201; 250,247; || 558| Victoria Blue R .....| 517,473. 
262,680; 421,049. || 559| Victoria Blue B ......| 297,413; 207,414; 
S25 Ready Violets RS ..... 204,797; 204,798. 496,435; 658,504; 
526|Acid Violet 4 RS ....| 294,797; 204,798. 684,457. 
527|Acid Violet 4 BN ....| 331,964; 331,965; || 560|Night Blue ...... eoee| 647,260; 658,504. 
é 580,186. 561|Acid Violet 5 BNS ..]} 603,016. 
528|Fast Acid Violet 10 B.| 501,069; 580,186; || 562|Fast Acid Blue B ....| 506,918. 
611,628. 563|New Patent Blue B ..| 605,119. 
s29!Acid Violet 6 B...... 564|Naphthalene Green V..| 628,243; 630,224; 
530|Acid Violet 6 B ......| 707,813. | 639,976; 639,977. 
531|Eriocyanin A ........| 464,538. s6s(Acid Blue B ........ 603,016. 
532|Alkali Violet 6 B . 340,022. 566| Wool Green S .......| 897,888; 891,889. 


533|Acid Violet 7 BN ....|] 353,264; 353,265. || 567) Wate Blite. «vcecsee| 476,483; 


sza4\Acid Violet 7 B...... 353,266 


DIGEST OF PATENTS 


N N 
= 6 NAME Patent No. E S NAME Patent No. 
Zr \[o 
Z iA 
WY } 
Group VIII—XANTHONE. (Abstract, Group XIX.) 
SOS) PivirOninwe Gueeee cee ae 445,684. sSellratiin Meee eles ene 
KROQ Acridin Red Bunce. s 586(Chrysolint <saescree eee 
70 RHOGAMIN: OL st ateets eae 402,4303- 425,504. 1 587| osin Goss. ..ceee nee 
By | ehodantin OF Goi ot. see 516,584; 516,585. || 588|Eosin, spirit sol....... 
Roi HOGAMIM) Gr eele siete eres 516,588. 580] BosiniS tesa stasis 
573|Rhodamin ae melcetesrete 377.3405 3775350. |, S00) Hosine BIN acces aie 
57 AR HOGaAmIN 93) ES cece eps 499,927. 591|Erythrosin, Yellowish. 
575|Rhodin 12 bu Ste we 592|Erythrosin, bluish .... 
576|Rhodamin 3G ....... 584,119. 593 Phloxin Po a.-6 eee 
g7ziRhodin’ 2. Giclees cas: 584,119. 594|Cyanosin, spirit sol ... 
578|Rhodamin 12 GF ....]| 613,113. 595|Rose Bengal ......... 
579|Sulfo Rhodamin B ... 506| Phloxin’ aeec <sterieieereers 
580|Fast Acid Violet B .. 597|Rose Bengal ......... 
581|Fast Acid Eosin G ...| 642,893. 598|Cyanosin B .....05 255 
582|Fast Acid Violet A 2 R 9|Gallemm A.) eae 
583|Acid Rosamin A ..... 600|Gallein® a... 2 se oie eet 
584|Fast Acid Blue R . 60r|Coeruléin® o22 sepa 
Grove IX.—ACRIDIN. (Abstract, Group I.) 
602|Acridin Yellow G ....] 675,568; 730,771; {|605|Benzoflavin .......-..| 382,832; 395,080; 
739,117 § 1,255,739; bey 537:723- 

Mr 1,455,486; 1,455,487. || 606|Phosphin E .......... 
603|Acridin Orange NO ..] 503,305; 537,723; || 607|Rheonin ..... ice SORSe hes 546,177. 

ie 1,455,486; 1,455,487. || 608|Euchrysin ........ es 
604|Acridin Orange R ....! 503,305; 537,723. ) 609| Homophosphin re ee 

Group X.—QUINOLIN. (Abstract, Group XIII.) 
610|Quinolin Red ........ 257,717. 613|Quinolin Yellow, aq. 
611|Quinolin Binewsoee: «-| 844,804. |>-'sol Saiceeeeeen covet 290,585; 800,588; 
612|Quinolin Yellow, sp. . | 1,197,632. 
SO) Scctureteioneia te eraikecaterats 290,585. | 
Group XI.—THIOBENZENYL. (Abstract, Group XVII.) 

614|ChrominvGitysoes ae 617|Chloramin Yellow 
615\lhioflaviniio eer s,« 412,979. C,. GG nb. Sees | 
656|\Primulingtea seme csi nce: 406,952; 415,359. 618|'Thioflavin TT cise cab emi aes ovion 


Group XII.—INDOPHENOL,. 


619|Indophenol 261;5183) 263;341. 


eeeeeeeeosn 


Grove XIII.—OXAZIN AND THIAZIN. 


620|Capri Blue GON ..... 494,838. 
621 |(Cresyl= Blue tm. 4.5 oie : 
622|Delphin Blue B ...... 897,619; 936,247. 
623|Pyrogallol Cyanin sulfo| 898,039. 
624|Modern Violet N ... 863,907. 
£20|Galloey. Heliotrope ...}| 707,832; 898,040. 
626|Gallocyanin DH ..... 25457215 257 .4OO8 
366,357. 
627 aiadess Cyanine sera: 844,156 
628|Gallocyanin MS ...... 444,538; 534,809. 
629|Gallo Green DH ..... 807,182 
630|Gyanazurin i csras ns 929,350 
631|Chromocyanin V .... 613,578; 638,576; 
1,188,259 
632|Ultra Violet LGP ....| 901,657. 
633 )Indalizarina Ry jp os see 613,578; 662,224. 
634|Indalizarin Green .... 
635|Blue tooo TC 3..é92. 629,666; 962,712. 
636|Prune pure ...... nes = 890,57 4- 
637|Gallamin Blue .......] 410,733; 842,303; 
| 893,855; 902,154. 
638|Amido Gallamin Blue.| 898,842. 
639|Gallanil Violet R..... 420,164; 440,359; 
451,502; 1,268,455. 
640|Modern Azurin DH ..| 898,008; 1,268,455. 
641|Corein) RRViy..a. 5.28 518,458; 534,809; 
842,303; 895,635. 
642|Phenocyanin VS ..... 547,173; 707,833. 
643|Phenocyanin TV ..... 585,934. 
644|Ultracyanin R, B .. 616,622; 992,613. 
6asiGallaziny cameecee ee 531,148. 


(Abstract, Group VIII.) 


(Abstract, Group XI and XVI.) 


646|Corein AR ...... cps [Mea Bee 
647|Nitroso Blue MR .... 
648|Iris Blue lia... eave vee 
649|New Blue R ......... 252,273; 413,562; 
454,535. 
6so| New, Blue” Bree ae 
651|New Methylene 
ls Blue’ GG" says aes 442,680 
652|New Fast Blue F, H .| 499,243. 
653|Nile Blue A ........ 404,309; 431,541. 
654|Nile Blue 2 B.c..en. 
655| Muscarin= sees ace 413,562. 
656|Alizarin Green G ....] 548,158. 
657|Alizarin Green B .... 
6s8| Fast. Black Ayes 
659|Methylene Blue B ....] 204,796; 246,327; 
| 270,311; 323,514; 
| 362,592; 366,639; 
| 366,640; 384,480. 
660|Methylene Green O .. 
661|Thionin Blue GO ....| 362,592; 366,639; 
366,640. 368,716. 
662| Thiocarmin Ries. 434,493. 
663|New Methylene Blue N]| 469,329. 
664|Leuco Gallothionin DH} 842,303. 
665| Urania’ Blue’ 3.22 .. ove} 607,408. 
666|Indochromogen § ....] 524,322. 
667|Brilliant Alizarin Blue] 522,897; 524,322; 
538,183; 560,795; 
606,212. 


NAME Patent No. 


Group XIV.—AZIN. 


668|Flavindulin O, II ... 543,784. 

669) Neutral “Violet ....-.. 248,246; 249,136. 

G70) NeutraledRed as a0 oc os « 249,13 

671|Indulin Scarlet ...... 533,829 

O72\Azocarmin» Ge....<..-| 428,530; 430,975; 
431,404; 466,852; 
524,222. 

673)Azocarmin B-........| 466,826; 567,473. 

674|Rosindulin 2 G ...... 443,408. 

675|Rosindulin G....... ‘ 443,408. 

676|Neutral Blue ........ 

677|\Basle Blue R ........ 360,764. 

678|Fast Neutral Violet B.| 248,246. 

67 Oatranin A i. oes 02 palee}i O25 120. 

py a panes Violet”... 

681|Methylene Gray O ...| 420,311; 636,626. 

GselNigtamin ys ca. 2st eas 

683|Safranin MN ........ 

684|Rhodulin Violet ......| 543,894; 557,022; 
559,062; 559,063; 
592,608. 


Group XV.—SULFUR. 


706|Cachou de Laval .....{ 897,873; 909,151; 


909,1555 1,244,795; 


1,244,796. 
707|Sulfin Brown ........ 


708|Sulfanilin Brown 4 B.| 687,581; 909,151. 
709|Italian Green ........ 
710|\Immedial Yellow D ..| 561,277; 712,747. 
711|Immedial Orange N...| 641,954; 714,542; 
895,037; 896,916. 
712|Kryogen Yellow G ...| 773,346. 
713|Thiophor Bronze 5 G. 
714|Thiophor Yellow 
BLONZee neck ccs cues 
715|Thiocatechin .........| 561,276; 687,072; 
738,027. 
716|Kryogen Yellow R ...| 773,346. 
717|Vidal Black I ...... «-| 532,484; 532,503; 
594,105; 653,278. 
718|St. Denis Black B ....| 646,873; 740,465. 
719| it hional “Black ....... 
720|Sulfur Black T ...... 618,152; 655,659. 
P2Tloulturs Diack. 5.6.4 
722|Auronal Black N ....| 606,193; 1,026,881. 
723|Autogen Black EEB ..| 904,224. 
724|Immedial Black FF ..| 610,541; 628,607; 
628,609; 635,169; 
639,806; 642,256; 
650,293; 651,077; 
667,689; 692,174; 
695,835. 
725|Immedial Dark 
Brown A e@eoeoeveeveee 596,559; 647,846; 
660,058; 660,067. 
726|Pyrogen Direct Blue .| 665,726; 775,570. 
727|Auronal Black B .....| 764,733; 764,734; 
764,735- 
728|\|Immedial Pure Blue ..| 653,670; 693,632; 
| 693,633; 693,634; 


Grove XVI.—ANTHRAQUINONE. 


SCHULZ INDEX 583 
iN 
SS NAME Patent No. 
et 
OG 
(Abstract, Group V.) 
685|Tannin Heliotrope ... 
686|Amethyst Violet ..... 
687|Rosolane O ..... ties 
688|Rosolane ..... ae beels 
HaoiPhvokvA~re Nik Ae eemae 395,300; 578,093. 
690|Diphene Blue R ..... 511,653. 
691|Metaphenylene Blue B] 395,300. 
692|Naphthazin Blue ..... 
693|Milling Blue ......... 
694|Rose Magdala ....... 
695|Paraphenylene Violet . 
696|Indamin Blue ........| 418,916. 
697|Indulin, spirit sol ....| 900,302. 
698|Nigrosin, spirit sol ... 
699|Indulin NN ...... as 
FOO NISTOSIN ee Wes ols hicks 0 0 
701|Paraphenylene Blue R. 392,723; 524,677. 
7o2|Para. Blue 5.555500 458,281. 
Wea RUD LCANTITI Me ae iereelea oat 
weal Atigamin ia. WA. wace sce 
TOSWLNC AMIN nGi Re eves wate 6 
(Abstract, Group XV.) 
710,766; 727,387. 
729|Kryogen Pure Blue R| 679,199; eh als 
778,713. 
730|Pyrogen Black G_....| 665,547. 
731|Thiophor Indigo CJ ..| 736,403; 778,478; 
821,378. 
732|Autogen Black .......| 646,873. 
733|Immedial Indone «| 709,151. 
734|Pyrogen Yellow M ... 
735|Pyrogen Indigo .....| 708,662; 723,154. 
736|Thion Blue B ........| 695,533; 695,534. 
737|Cotton Brown .......] 640,559. 
738|Cotton Black ..... Be 644,959. 
739|Immedial Bordeaux G 701,435; 866,939. 
740|Fast Black B ........| 545,336; 545,337; 
611,112; 661,438. 
VAT Past. Blacks DS geses uae 546,576. ne 
742|Printing Blue for. Wool 609,327. 
743|Kryogen Brown A ... 609,327; 632,170; 
+137. 
Pi Gcitol Blac rier ae. |e atk 
745|Melanogen Blue ..... 640,218; 658,286; 
667,486, 
746|Thional Green B ..... ore ake 
747|Thional Brown G ....| 712,176. 
748|Hydron Blue R ...... 919,572; 931,598; 
6, , , a ed 
749|Anthraquinone Black . mas ht Leenks 
750|Kryogen Brown A ... : ; 4 
751|Kryogen Brown RB . 
752|Kryogen Direct 
Blue: GOoek . se'oas 
753|Kryogen Direct Blue B 
754|Kryogen Direct 
Blue aB ee ytecrec cs 
755|Kryogen Black BNX.. 
756|Kryogen Black TGO . 
757|Sulfogen Brown G ... 
(Abstract, Group III.) 
906,367. 


766|Indanthrene Violet R.. 


758|Sirius Yellow G ..... 968,376 
759|Anthraflavon G ......| 837,840 
760|Indanthrene Gold 
Orange: a.c sees F 856,811 
761|Indanthrene Gold 
CATED eas ot hose sas = + 055,105. 
762|Indanthrene Scarlet G.| 623,069; 955,105. 
763|Indanthrene Dark 
gh Gavoul 8) OMS ae one 818,992. 
764|Indanthrene Violet RD 8373795. 
765|Indanthrene Green B .! 796,393. 


767|Indanthrene Violet 2 R|/1,003,z€8. 
768|Indanthrene Violet B .|1,003,268. 


769|Alizarin Yellow C ...} 443,402; 
770|Alizarin Yellow A ...| 415,088; 
771|Resoflavin W ........ 618,000; 
772|\Galloflavin W ........ 348,613. 
773|Anthracene Yellow ... 
774|Alizarin Black WR ...| 368,054; 
631,614. 
775|Alizarin Dark Green W) 619,114; 


452,210. 
623,069. 
623,069. 
379,150; 
610,115; 


NAME 


Group XVI.—(Continued).—-ANTHRAQUINONE. 


rinting Black, for 
wool 
777|Chromogen I .. 
ye8| Alizarin VI .scersaiee 


776 


eceveee 


779|Alizarin Orange A ... 
780|Alizarin Red S .. 
781|Erweco Alizarin Red. 
782|Anthracene Brown W. 
783|Purpurin 

784|Alizarin SX .... 
78s5|Alizarin GI 
786|Alizarin Red 3 WS... 
787|Alizarin Bordeaux B.. 
788|Alizarin Cyanin R ... 
789|Anthracene Blue WR. 


eoee 


790|Acid Alizarin Blue BB 
791|Indanthrene Olive G .. 
792|Cibanone Orange R .. 
793|Cibanone Blue 3 G ... 
794|Cibanone Black B .... 
795|Cibanone Yellow R .. 
796|Acid Alizarin Green G 
797\Alizarin Garnet R ... 
798|Alizarin Maroon W .. 
Hed beat Cyanin G .... 
800|/Anthracene Blue WG. 
Sor bantutees Blue WGG 
802|Anthracene Blue WG, 
1S OW) capects = Pe coe 
803|Alizarin Blue X 
804|Alizarin Blue S ...... 


8o05|Alizarin Green S .. 
806|Alizarin Black P ..... 
807|Alizarin Black S ..... 
808|Alizarin Green X .... 


809|Alizarin Indigo Blue S 
810|Helindone Yellow 
GINS Beteletenn 9 aca ah Ne 
8r1|Algol Yellow 3 G.... 
812|Indanthrene Orange RT 
813|Indanthrene Copper R 
814|Algol Yellow WG .... 
815|Algol Scarlet G ...... 
816|Algol Red 5 G ... 
_ 817|Algol Yellow R ...... 


e 
oe 


818| Algol Rose R ....eeee 
819|Algol Red R ...-eeee 
820| Algol Brilliant 
Violet R 
821|Algol Brilliant 
Violet BB 


| 


esoceoveeeees 


DIGEST OF PATENTS 


609,327. 


Patent No. 


95,465; Re. 4,321; 
97,597; Re. 4,558; 


127,426; 
154,153; 
1,036,880; 
t.260,152:; 
186,032. 
95,465. 
826,500. 
686,356. 
186,032; 


446,893. 
446,892. 
502,603; 
506,265; 


922,282. 


902,895. 


476,410; 
502,603; 
654,506. 
617,686. 


654,505. 
186,032; 
258,530 
274,081; 
399479. 


399,479; 
399,481; 
401,635. 
399,482. 


938,566. 
925,917. 
925,917. 


938,616; 
972,066; 


935,781. 


957,039; 
957,041; 


153,536; 
885,577; 
1,036,881; 


188,061. 


503,295; 
519,229. 


476,420. 
617,686; 


569,405. 
258,531; 
527,457- 


399,480; 
401,633; 


938,617; 


957,040; 
957,042. 


Grove XVII.—INDIGO. 


874|Indigo ... 


eoeovoaoeeoeoee 


227,470; 
233,458; 
233,460; 
240,359 
240,042; 
250,036; 
251,500; 
257,812; 
257,814 


228,300; 
233,459; 
235,193; 
240,041; 
250,035; 
251,499; 
251,671; 
257,8133 
259,260; 


NAME 


822|Algol Brilliant 
Oranges ERY oyu vee 


823|Algol Violet B ....... 


824|Algol Orange R ...... 
S2slAlgol Red By .2...cen 
826|Indanthrene Red G ... 
827|Indanthrene Bor- 
deaux Bocas Se pry 
828|Indanthrene Bordeaux. 
829| Algol Bordeaux 3 B.. 
830|Indanthrene Red R .. 
831|Indanthrene Red BN.. 
832|Indanthrene Violet RN 
833|Algol Olive R ... 


837|Indanthrene Blue R .. 


838|Indanthrene Blue RS. 
839|Algol Blue K 
840|Indanthrene Blue 3 G. 
841|Indanthrene Blue 2 GS 
842|Indanthrene Blue GCD 
843\|Indanthrene Blue GC. 
844| Algol Blue 3 G ...... 
845|Indanthrene Maroon R 
846|Indanthrene Dark Blue 
847|Algol Green B ....... 
848|Indanthrene Gray B .. 
849|Indanthrene Yellow G. 
8so|Indanthrene Blue WB 
8s1|Alizarin Direct Blue B 
852|Alizarin Irisol D 
853|Anthraquinone Violet.. 
854|Alizarin Viridin DG... 


855|Alizarin Pure Blue B. 
856|Alizarin Astrol B .... 
857|Erweco Alizarin 
Blue Rir cesar ws eiheren 
858|Alizarin Saphirol B .. 
8s09|Cyananthrol (R’ cys. ee. 
860|Cyananthrol G ....... 
861|Anthraquinone Blue SR 
862|Alizarin Blue Black B. 
863|Anthraquinone Blue 
Green 
864] Anthraquinone | 
Green 
865|Alizarin Cyanin 
Green 


866|Leucol Dark Green B. 
867|Indanthrene Brown B. 
868|Cibanone Brown B ... 
869|Algol Brown B ...... 
870|Algol Corinth R ..... 
871|Indanthrene Violet RN 
872|Leucol Brown B ..... 
873|Helindone Brown AN. 


(Abstract, Group VII.) 
| 


eorereeeeee 


eoeeeeeees 


Patent No. 


(Abstract, Group III.) 


957,040; 
957,042. 
957039; 
957,041; 
814,137. 
875,390. 
863,397. 


961,612. 
863,397. 
950,344. 
863,397. 
1,011,068. 
961,048. 


957,041; 


957,040; 
957,042. 


971,225;Re.13,257. 


960,182. 


958,325. 
682,523; 
724,789; 
682,523. 
775,368. 
970,878. 
948,204. 
753,659. 
739,579- 
801,418. 
791,869. 
809,892. 
7753367. 
767,259. 
739,145. 
724,789. 
734,866; 
599,426; 
659,565; 
599,426; 
603,659; 
599,426; 
599,426; 


996,487. 
595,349- 
715,662. 
715,662. 
632,621. 
599,425; 


599,426; 
654,295; 
874,744. 
876,190. 
915,385. 


874,743. 
943,717- 


259,261; 
262,605; 
540,427; 
617,651; 
618,006; 
619,884; 
620,563; 
622,139; 
643,502; 


-|1,025,195; 1,038,003. 


692,762; 
855,248. 


748,375. 
599,427. 
650,566. 
599,427; 
734,325. 
599,427. 
599,427. 


749,973. 


599,427; 
754,768. 


259,629; 
276,888; 
546,165; 


SCHULZ INDEX 585 


N 
ie 
OG 


Wn 


N 

= é NAME Patent No. NAME Patent No. 
a4 

n 


Grove XVII.—(Continued).—INDIGO. (Abstract, Group VII.) 


646,841; 647,263; 662,073. 
647,279; 647,280; || 889/Indigo Yellow 3 G ...| 994,088; 1,026,574. 
647,281; 651,453; |] 890/Ciba Yellow G .......] 907,766; 1,074,850. 
657,539; 661,871; || 891|Ciba Green G ....... 872,227; 960,098. 
662,076; 662,703; || 892|Helidone Green G ....| 932,334. 
662,754; 662,755; |} 893|Alizarin Indigo G ....| 961,396; 980,140; 
669,794; 671,3445 999,439. 
673,887; 675,217; || 894|Alizarin Indigo B ....| 998,506. 
680,395; 690,332; || 895|Alizarin Indigo 3 R ..| 958,464; 958,465; 


| 697,545; 698,328; 961,397; 961,398; 
| 699,581; 704,804; 961,399; 999,439. 
| 712,190; 712,793; || 896|Helindone Blue 3 GN. |1,025,174. 

714,000; 714,042; || 897|Ciba Heliotrope B ...] 876,158; 808,452; 
| 727,270; 731,3853 | 1,074,505; 1,266,092. 

737,836; 746,965; || 898|Helindone Violet D ..|1,028,911. 

760,171; 7Ol,440; 4) Sog|Ciba Gray G .2...... 954,273. 

768,455; 772,560; || goo|Ciba Violet 3 B ...... 836,300; 848,356. 

772,775; 776,884; || 901(Ciba Violet B ........ 836,300; 848,355; 

778,725;  778,7523 848,356. 

818,341; 839,099; || 902|Helindone Brown 2 R.! 968,697. 

841,456; 850,444; || 903|Helindone Brown 5 R.| 955,609; 968,697. 
| 860,900; 868,294; || 904|Helindone Brown G ..| 955,699; 968,607. 
| 868,755; 891,708; || 905|Thio Indigo Scarlet R.| 841,003; 874,649; 


937,194; 960,671; | 923,959; 943,678. 
063,677; 984,442; || 906|Thio Indigo Scarlet G.| 848,355; 867,714; 
1,012,363; 1,015,495; 874,649; 887,600; 


1,211,413; 1,442,743. } 899,994. 
87s|Indigo Salt T .......| 257,815; 540,427. ||907|Ciba Scarlet G ......| 891,690; 904,867; 
876|Indigo White, 20 per bee 965,170. 
1) eee Desgueess| $94,579; 906,307. || 908|Ciba Red R .......- «| OF5,3946. 
877|Indigo Carmine ......| 251,501; 524,256; ||909|Ciba Red B ......... 848,354; 899,152. 
540,564; 726,688. || 910|Helindone Rose BN ..| 892,897; 947,030. 
878\Indigotin P ..........| 524,256. 911|Ciba Orange G ......|1,081,808. 
879!Brom Indigo .........| 715,074; 729,217; || 912|Thio Indigo Red B....| 819,348; 831,844; 
730,148; 807,782. 850,827; 868,205; 
880!Helindone Blue BB ..| 706,921; 856,687; 877,743; 894,004; 
883,703; 888,230. 894,005; 894,006; 
881|Dianthrene Blue 2 B..| 706,927; 856,776; 910,839; 943,560} 
937,040; 937,041. : 949,592. 
1,043,468. 913|Helindone Orange R..| 867,305; 881,157; 
8R2\Indigo 5 B ..........|1,043,468; 1,070,541. ; 881,158; 943,561. 
883lIndigo 6 B ....... ..-|1,043,468,; 1,061.781. || 914|Helindone Orange D..| 872,585; 963,813. 
884|Brilliant Indigo 2 B...| 872,115; 948,241; ||915|Helindone Fast Scarlet} 963,813. 
1,043,468. 916|Helindone Scarlet S ..| 867,306. 


88s5|Brilliant Indigo B ....| 761,007; 812,598; ||917|Helindone Red B ....| 916,020; 916,030. 
1,042,679; 1,043,468; || 918|Helindone Red 3 B ..| 916,029; 916,030. 
1,050,179. 919(/Ciba Bordeaux B ....| 867,715. 
886|Brilliant Indigo G ....| 955,410; 1,043,468. || 9720|Helindone Violet BB.. |1.025.128. 
887|Brilliant Indigo 4 G ..| 872,115; 957,683; || 921|Helindone Gray 2 B..| 872,085; 872,086. 
1,043,468. | 959,617. 
SSRIINGIZO! bsicnis ss aes aides 2700002) 020.442 ° | 


Group XVIII.—ANILIN BLACK. (Abstract, Group IT.) 


922|Anilin Black ........{ 35,589; 79,942; f)922|Anilin Black (contd.).{ 529,498; 520,499; 
96,242; 111,654; 789,221; 992,047; 

138,155; 180,538; | 1,326,367. 

193,158; 387,097; |} 923 fabs Dipeenessncens sd 200,000) 1,105,554; 


| | 


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